CN103732629A - Addition-fragmentation agents - Google Patents

Addition-fragmentation agents Download PDF

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CN103732629A
CN103732629A CN201280040201.3A CN201280040201A CN103732629A CN 103732629 A CN103732629 A CN 103732629A CN 201280040201 A CN201280040201 A CN 201280040201A CN 103732629 A CN103732629 A CN 103732629A
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methyl
addition
clastogen
alkyl
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CN103732629B (en
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G·D·乔利
A·S·阿比尔雅曼
B·D·克雷格
A·法尔萨菲
J·D·奥克斯曼
L·R·克雷普斯基
W·H·莫泽
S·尤特
A·R·弗诺夫
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Shuwanuo Intellectual Property Co
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3M Innovative Properties Co
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
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    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Abstract

Addition-fragmentation agents of the formula are disclosed having the following functional groups: 1) a labile addition-fragmentation group that can cleave and reform to relieve strain, 2) a free-radically polymerizable group, and 3) a surface-modifying functional group that associates with the surface of a substrate.

Description

Addition-clastogen
the cross reference of related application
The application requires the rights and interests of the U.S. Provisional Patent Application 61/526470 of submission on August 23rd, 2012, and its disclosure is incorporated to herein in full with way of reference.
Background technology
The invention provides the novel addition-clastogen for low-stress polymerisable compound.Raolical polymerizable is along with conversion of monomer is polymkeric substance and reducing with volume conventionally.Volumetric shrinkage produces stress in curing composition, thereby causes tiny crack and distortion.Transfer to the stress on interface between curing composition and matrix and may cause adhesion failure, and may affect the weather resistance of curing composition.
Addition-clastogen of the present disclosure by comprise can be during polymerization process the labile crosslinking of cracking restructuring stress relieving is provided.Crosslinked cracking can provide such mechanism, and it allows network reconfiguration, eliminates polymerization stress, and suppresses the development of high stress areas.Addition-clastogen of the present invention also can be put stress relieving is provided by delay gelatinizing, and at described jellying point place, polymerisable compound changes Hookean body into from viscous material.Polymerizable mixture keeps the time of thickness longer, streams can be during polymerization process the usable time of relieve stresses just more.
Addition-clastogen provides novel stress drop low cross-linking agent, and this stress drop low cross-linking agent can be used for dental composition, film, hard coat, matrix material, tackiness agent and stands in other application of stress reduction.In addition, addition-breaking-down process causes chain failover events, and described event provides new polymers that can be further functionalized.
Summary of the invention
The disclosure provides addition-clastogen, described addition-clastogen has following functional group: 1) unsettled addition-fracture group, described addition-fracture group cleavable restructuring are to eliminate strain, 2) group of free redical polymerization, and 3) with the surface modification functional group of the surface association of substrate.In addition addition-clastogen crosslinkable polymer.
Addition-clastogen can be added in polymerizable monomer mixture to reduce the stress of polymerization induced.In the embodiment of Z >=2, this reagent is also as addition-fracture linking agent, now crosslinked unstable.The disclosure also provides the method with addition-clastogen of a kind of preparation formula I, as further disclosed herein.
The disclosure also provides a kind of curable compositions, the monomer that described curable compositions comprises addition-clastogen and one or more free redical polymerizations, and described addition-clastogen provides the stress of resulting polymers to reduce.Described addition-clastogen serves as chain-transfer agent via addition-breaking-down process, thereby is cross-linked unstable between polymerization period and continuous cracking restructuring, thereby provides the stress based on polymerization to reduce.
The disclosure also provides a kind of curable compositions, and described curable compositions has and will be bonded to or associate to the surface modification functional group of substrate surface.As a result, curable compositions of the present disclosure is self-adhesive or from primary coat.
As used herein:
" acryloyl " used with general significance, and not only refers to acrylic acid derivative, also refers to respectively sulfonamide derivatives and alcohol derivate;
" (methyl) acryloyl " comprises acryloyl and methacryloyl; That is, comprise ester and acid amides.
" curable " refers to that the material converting that can apply by means of radical polymerization, chemically crosslinked, radiation crosslinking etc. becomes the immobilising material substantially of solid.
" alkyl " comprises straight chain, branching and cyclic alkyl group and comprises the alkyl group that does not replace and replace.Except as otherwise noted, described alkyl group comprises 1 to 20 carbon atom conventionally.As used herein, the example of " alkyl " includes but not limited to methyl, ethyl, n-propyl, normal-butyl, n-pentyl, isobutyl-, the tertiary butyl, sec.-propyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, suberyl, adamantyl and norcamphyl etc.Except as otherwise noted, alkyl can be monovalence or multivalence, i.e. univalent alkyl or multivalence alkylidene group.
" assorted alkyl " comprises having one or more heteroatomic straight chains independently selected from S, O and N, branching and cyclic alkyl group, and described alkyl group comprises the alkyl group that does not replace and replace.Except as otherwise noted, described assorted alkyl group comprises 1 to 20 carbon atom conventionally." assorted alkyl " is the subset of " alkyl that comprises one or more S, N, O, P or Si atom " hereinafter described.As used herein, the example of " assorted alkyl " includes but not limited to methoxyl group, oxyethyl group, propoxy-, 3,6-dioxaheptyl, 3-(trimethyl silyl)-propyl group, 4-dimethylamino butyl etc.Except as otherwise noted, assorted alkyl group can be monovalence or multivalence, i.e. the assorted alkyl of monovalence or the assorted alkylidene group of multivalence.
" aryl " is for the aromatic group that comprises 5-18 annular atoms and can comprise optional condensed ring, and it is saturated, undersaturated or aromatics that this condensed ring can be.The example of aromatic yl group comprises phenyl, naphthyl, biphenyl, phenanthryl and anthryl.Heteroaryl is the aryl that comprises 1-3 heteroatoms such as nitrogen, oxygen or sulphur and can comprises condensed ring.Some examples of heteroaryl groups be pyridyl, furyl, pyrryl, thienyl, thiazolyl,
Figure BDA0000466800920000031
azoles base, imidazolyl, indyl, benzofuryl and benzothiazolyl.Except as otherwise noted, aryl and heteroaryl groups can be monovalence or multivalence, i.e. monovalence aryl or multivalence arylidene.
" (mixing) alkyl " comprises alkyl alkyl and aromatic yl group, and the assorted alkyl of assorted alkyl and heteroaryl groups, and the latter comprises oxygen heteroatom in one or more chains, such as ether or amino group.Assorted alkyl optionally comprises in one or more chains (in chain) functional group, and described functional group comprises ester, acid amides, urea, carbamate and carbonate functionalities.Except as otherwise noted, non-polymeric (mixing) hydrocarbyl group comprises 1 to 60 carbon atom conventionally.Except above for those described in " alkyl ", " assorted alkyl ", " aryl " and " heteroaryl ", as used herein, some examples of this type of assorted alkyl also include but not limited to methoxyl group, oxyethyl group, propoxy-, 4-diphenyl amino butyl, 2-(2'-phenoxy group oxyethyl group) ethyl, 3,6-dioxaheptyl, 3,6-dioxa hexyl-6-phenyl.
Accompanying drawing explanation
Fig. 1 is the fertile thatch contractible graph of the curable compositions of example.
Embodiment
The disclosure provides addition-clastogen, described addition-clastogen has following functional group: 1) unsettled addition-fracture group, described addition-fracture group cleavable restructuring are to eliminate strain, 2) the surface modification organo-functional group group of free redical polymerization, and 3) associating with substrate surface.In certain embodiments, addition clastogen crosslinkable polymer.
Addition-fracture group allows polymeric system crosslinked, and wherein, unstable group can be added into, disconnect and again add by the polymer chain of growth, to reduce the polymkeric substance of growth or the stress of polymer network.This type of group can be people such as being selected from G.Moad, free radical addition during Radical addition-fragmentation chemistry in polymer synthesis(polymkeric substance is synthetic-fracture chemistry), Polymer(polymkeric substance), the 49th the 5th phase of volume, (on March 03rd, 2008), those described in 1079-1131 page.
In a preferred embodiment, the disclosure provides the addition-clastogen of following formula:
Figure BDA0000466800920000041
Wherein
R 1, R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group, precondition is R 1, R 2and R 3in at least one be Z m-Q-, and precondition is R 1, R 2and R 3in at least one be Y p-Q '-,
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y is the functional group of surface modification, and described functional group and the substrate that described addition-clastogen is set on it are associated;
M is 1 to 6;
P is 1 or 2;
Each X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.It is also understood that R 1, R 2and R 3in each comprised Z m-Q-and Y p-Q '-group both, polymerizable groups and surface-modifying groups are a part for identical " R " group.
The disclosure provides the addition-clastogen as above-mentioned formula I: the unsaturated part Z of ethylenic of monomer can include but not limited to following structure, comprise (methyl) acryloyl, vinyl, vinylbenzene and ethynyl, the described structure reference below preparation of compound is described more all sidedly.
Figure BDA0000466800920000051
R wherein 4for H or C 1-C 4alkyl.
In addition about formula I, especially available Y group (R 1-X 1-group and optionally R 2-X 1-and R 3-X 1group) comprise that phosplate, phosphonic acid ester, phosphonic acids, hydroxamic acid, carboxylic acid and etheric acid root, acid anhydrides, isonitrile group, silyl, disulphide, mercaptan, amino,-sulfinic acid, sulfonic acid, phosphine, resol (comprise catechol and 1,2,3-trihydroxybenzene derivative) or heterocyclic aromatic group.Special concern be that Y is selected to an accepted way of doing sth-SiR 7 3silyl-group, each R wherein 7group is independently selected from alkoxyl group, acetoxyl group and halogen ion.
It is believed that addition-clastogen follows the addition-fracture approach shown in following scheme 1.In this scheme, the linking agent of formula I is shown, wherein n is 0.In step 1, free radical Substance P adds in linking agent.Then as shown in step 2, linking agent breaks to form the tertiary free radical of stable alpha-carbonyl, and the alpha, beta-unsaturated esters with free radical Substance P residue.This alpha, beta-unsaturated esters can experience the free radical addition as shown in step 5.Free radical addition can be caused by initiator or free polymer readical.
Meanwhile, the polymerization that the tertiary free radical of alpha-carbonyl can trigger monomer, as shown in step 3.For illustrational object, show methacrylate monomer.When monomer addition, produce the free radical intermediate of methacrylic ester end-blocking.Under the existence of formula 1 linking agent (as shown in step 4), there is addition and rupture both, produce tertiary free radical.
scheme 1:
Figure BDA0000466800920000061
As shown in following scheme 2, addition-fracture linking agent is provided for multiple potential stress relief mechanisms.The methacrylate polymers that simplification is shown is crosslinked by rupture two " Z " groups of linking agent of addition.Key between the unsaturated Z group of ethylenic will form unsettled crosslinked.The fracture of addition-fracture linking agent provides the mechanism of crosslinked cracking.The cracking of labile crosslinking can allow the lax or restructuring of polymer network, especially in high stress areas, thereby provides potential stress relief mechanisms.
scheme 2
Figure BDA0000466800920000071
Under the existence of addition-fracture material, stress relieving also can be the result of speed of reaction decay (slower solidification rate).Free radical is added and in addition-fracture linking agent, generated tertiary free radical of potential long lifetime (product of step 1, scheme 1).This long-life free radical intermediate can be returned to initial substance, add in monomer or segment.If fracture, contrary addition and monomer additional phase are slower for addition, the tertiary free radical of intermediate will be relatively long-life.Then, this long-life free radical intermediate will serve as free radical reservoir, thereby overall polymerization process is slowed down.The solidification rate of decay can contribute to delay material and change Hookean body into from viscous material, thus delay gelatinizing point.Rear gel is punctured into the main composition factor of stress development; Therefore, delay gelatinizing point just can be by allowing material additional flow for some time during solidification process to cause stress relieving even slightly.Therefore,, even if there is the compound of the formula I of single Z group, also can be used for reducing polymerization stress.
The compound of formula I can be prepared by replacement, displacement or condensation reaction by (methyl) acrylate dimer and tripolymer.Initial (methyl) acrylate dimer and tripolymer can be by being used U.S.4,547, the method of 323 (Carlson), under the existence of radical initiator, make (methyl) acryloyl monomer and cobalt (II) complex catalyst free radical addition and make, described document is incorporated herein by reference.Alternatively, (methyl) acryloyl dimer and tripolymer can be used U.S.4,886,861 (Janowicz) or U.S.5, the method for 324,879 (Hawthorne), use cobalt chelated complexes to be prepared, described document is incorporated herein by reference.In any method, reaction mixture all can comprise the complex mixture of dimer, tripolymer, higher oligomer and polymkeric substance, and can be by distillation, the dimer of expectation or tripolymer is separated from mixture.
With reference to formula I, required ethylenic unsaturated " Z " group can be by comprising that the mode of addition, condensation, replacement and replacement(metathesis)reaction mixes in (methyl) acryloyl dimer or tripolymer.In general, (methyl) acryloyl dimer or trimerical one or more carboxyl groups are provided with the Z-Q-X of formula I 1group.
More specifically, make (methyl) acryloyl compound of following formula:
Figure BDA0000466800920000081
X wherein 2comprise electrophilic or nucleophilic functional group,
X 3for X 2, X 1-R 2or X 1-R 3, and
N is 0 or 1;
React with the coreactivity compound of following formula:
Figure BDA0000466800920000082
with
Figure BDA0000466800920000083
Wherein
A 1and A 2respectively do for oneself and the X of functional group 2the functional group of coreaction, R 4for hydrogen, C 1-C 4alkyl group, R 5and R 5* respectively do for oneself ethylenic unsaturated group is engaged to reactive functional groups A 1and A 2singly-bound or divalence or trivalent (mixing) alkyl linking group, and x is 1 or 2.As the result of reaction, addition-clastogen is provided with the group Z of free redical polymerization and the Y of functional group of surface modification.Be to be understood that, with reacting of the compound of formula III a and formula III b can be simultaneously or order, and the stoichiometry of selective reaction thing makes the addition-clastogen of gained on average have the group Z of at least one free redical polymerization and the Y of functional group of at least one surface modification.
Preferably, make the compound of formula II and A wherein 1the formula III a compound reaction that comprises epoxy-functional or aziridine functional group.Except the group Z of required free redical polymerization, reaction product also has can be further functionalized so that hydroxyl or the amido of the required Y of surface modification functional group to be provided.
More specifically, R 5and R 5* respectively do for oneself ethylenic unsaturated group is connected to singly-bound on co-reactive functional group A or the linking group of divalence or trivalent, and preferably comprise 34 at the most, preferably at the most 18, more preferably 10 carbon atoms at the most, and optionally comprise oxygen and nitrogen-atoms, ester, acid amides, urea, carbamate and carbonate group in optional chain.Work as R 5or R 5while being * not singly-bound, be selected from-O-,-S-,-NR 4-,-SO 2-,-PO 2-,-CO-,-OCO-,-NR 4-CO-, NR 4-CO-O-, NR 4-CO-NR 4-,-R 6-and their combination, such as-CO-O-R 6-,-CO-NR 4-R 6-and-R 6-CO-O-R 6-.
Each R wherein 4for hydrogen, C 1-C 4alkyl group or aromatic yl group, each R 6for have 1 to 6 carbon atom alkylidene group, there are 5 or 6 yuan of cycloalkylidene groups of 5 to 10 carbon atoms, or there is the divalent aromatic radical of 6 to 16 carbon atoms; A 1for reacting to mix with co-reactive functional group the reactive functional groups of sense " Z " group of free redical polymerization, and A 2for reacting to mix with co-reactive functional group the reactive functional groups of sense " Y " group of surface modification.
Should be appreciated that the X of formula II 2the A of group and formula III 1reaction between group will form the Z of formula I m-Q-X 1-part, so can be defined as-R of Q 5-A*-X 2*-, A wherein 1*-X 2*-be A 1and X 2between the key that forms, as mentioned above.Therefore Q can be defined as singly-bound or divalence connection (mixing) hydrocarbyl group.More specifically, Q is for to be connected to singly-bound or the divalent linker on co-reactive functional group A by ethylenic unsaturated group, and preferably comprise 34 at the most, preferably at the most 18, more preferably 10 carbon atoms at the most, and optionally comprise oxygen and nitrogen-atoms, ester, acid amides, urea, carbamate and carbonate group in optional chain.When Q is not singly-bound, its can be selected from-O-,-S-,-NR 4-,-SO 2-,-PO 2-,-CO-,-OCO-,-R 6-and their combination, such as NR 4-CO-NR 4-, NR 4-CO-O-, NR 4-CO-NR 4--CO-O-R 6-,-CO-NR 4-R 6-and-R 6-CO-O-R 6-,-O-R 6-,-S-R 6--,-NR 4-R 6-,-SO 2-R 6-,-PO 2-R 6-,-CO-R 6-,-OCO-R 6-,-NR 4-CO-R 6-, NR 4-R 6-CO-O-, NR 4-CO-NR 4-,-R 6-, precondition is that Q-Z does not comprise peroxide bridge, i.e. O-O, N-O, S-O, N-N, N-S key, wherein each R 4for hydrogen, C 1-C 4alkyl group or aromatic yl group, each R 6for have 1 to 6 carbon atom alkylidene group, there are 5 or 6 yuan of cycloalkylidene groups of 5 to 10 carbon atoms or there is the divalence arylene group of 6 to 16 carbon atoms.
Similarly, the X of formula II 2the A of group and formula III b 2reaction between group will form the Y of formula I p-Q '-part.
Referring to formula I, especially available Z group (R 1-X 1-group and optional R 2-X 1-group) comprise H 2c=C (CH 3) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C (CH 3)=CH 2)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH (CH 2oC 6h 5)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2cH 2-N (H)-C (O)-O-CH (CH 2o C 6h 5)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and H 2c=C (H) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-.
Preferably, the compound that makes formula II and aziridine or epoxy functionalized (methyl) acryloyl react, as shown in scheme III.Should be appreciated that the different isomerization body in these descriptions can derive from ring-opening reaction.In scheme III, laterally methyl is represented as any one that is attached to adjacent carbons.So, have respectively amine or oh group shown in product can by with formula IIb:A 2-R 5* the compound reaction of-Y and be provided with the functional group of surface modification.For example,, product can be by being provided with the group of silyl surface modification with alkyl silyl isocyanate reaction.Note reacting with methylaziridine the mixture that also can cause acrylate and acrylamide product.
scheme III
More preferably, the compound that does not make formula II and aziridine or epoxy functionalized compound react to form the intermediate functional group as shown in scheme IV.In reaction scheme, product is further functionalized so that the group Z of required free redical polymerization to be provided, and the group Y of surface modification.That is, available hydroxyl and/or an amino part use the compound of formula III a functionalized, and another part is functionalized with the compound of formula III b.Alternatively, epoxy functionalized or aziridine functional polymer can further use the functionalized compound with preparation formula I of nucleophilic compound of formula III a or formula III b.
scheme IV
Figure BDA0000466800920000112
Or
Figure BDA0000466800920000121
Available reactivity (and coreactivity) (X of functional group 2and those of formula III a and formula III b) comprise hydroxyl, secondary amino group,
Figure BDA0000466800920000122
azoles quinoline base,
Figure BDA0000466800920000123
oxazolone base, acetylacetonate, carboxyl, isocyanato, epoxy group(ing), '-aziridino, acid halide group and cyclic anhydride group.Wherein (methyl) acrylate dimer/trimerical reactive functional groups is isocyanato functional group, and co-reactive functional group preferably includes primary amino or secondary amino group or oh group.When described reactive functional groups comprises oh group, described co-reactive functional group preferably comprise carboxyl, ester group, acid halide group, isocyanato, epoxy group(ing), acid anhydrides, azlactone base or
Figure BDA0000466800920000124
azoles quinoline base group.When described side chain reactive functional groups comprises carboxylic group, described co-reactive functional group preferably comprise hydroxyl, amino, epoxy group(ing), isocyanato or or azoles quinoline base group.In general, described reaction occurs between functional group nucleophilic and parent's electricity.
The representative example of available compound with the formula III a of co-reactive functional group comprises (methyl) hydroxyalkyl acrylate, such as (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid 2,3-dihydroxyl propyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester and (methyl) vinylformic acid 2-(2-hydroxy ethoxy) ethyl ester; (methyl) acrylic-amino alkane ester, such as the amino propyl ester of (methyl) vinylformic acid 3-and 4-amino-benzene ethene;
Figure BDA0000466800920000126
azoles quinoline based compound is such as 2-vinyl-1,3- azoles quinoline-5-ketone, 2-vinyl-4,4-dimethyl-1,3-
Figure BDA0000466800920000128
azoles quinoline-5-ketone, 2-pseudoallyl-4,4-dimethyl-1,3- azoles quinoline-5-ketone and 2-propenyl-4,4-dimethyl-1,3-
Figure BDA00004668009200001210
azoles quinoline-5-ketone; The compound of carboxyl substituted, such as (methyl) vinylformic acid and (methyl) vinylformic acid 4-carboxylic benzyl ester; The compound that isocyanato replaces, such as (methyl) vinylformic acid isocyanato ethyl ester and (methyl) vinylformic acid-4-isocyanato cyclohexyl; The compound that epoxy group(ing) replaces, such as (methyl) glycidyl acrylate; The compound that '-aziridino replaces, such as N-acryloyl aziridine and 1-(2-propenyl)-aziridine; And acryloyl halide compound, such as (methyl) acrylate chloride.
The functional compound that the representative hydroxyl of formula III a replaces comprises: hydroxyalkyl acrylate and hydroxyalkyl acrylamide, and such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, (methyl) 2-hydroxypropyl acrylate, the chloro-2-hydroxypropylmethyl of 3-(methyl) acrylate, 2-hydroxyethyl (methyl) acrylamide, 4-hydroxy-cyclohexyl (methyl) acrylate, 3-acryloxy phenol, 2-(4-(methyl) acryloxy phenyl)-2-(4-hydroxy phenyl) propane (also referred to as dihydroxyphenyl propane mono acrylic ester), 2-propine-1-alcohol and 3-butyne-1-ol.
The amino functional compound replacing of representativeness of formula III a comprises: 2-methyl aminoethyl (methyl) acrylate, 3-aminopropyl (methyl) acrylate, 4-aminocyclohexyl (methyl) acrylate, N-(3-aminophenyl) (methyl) acrylamide, N-(methyl) acryloyl quadrol and 4-aminophenyl-4-acrylamide phenylsulfone.
The functional compound that the representative azlactone group of formula III a replaces comprises: 2-vinyl-1,3-
Figure BDA0000466800920000131
azoles quinoline-5-ketone; 2-vinyl-4-methyl isophthalic acid, 3-
Figure BDA0000466800920000132
azoles quinoline-5-ketone; 2-pseudoallyl-1,3- azoles quinoline-5-ketone; 2-pseudoallyl-4-methyl isophthalic acid, 3-
Figure BDA0000466800920000134
azoles quinoline-5-ketone; 2-vinyl-4,4-dimethyl-1,3-
Figure BDA0000466800920000135
azoles quinoline-5-ketone; 2-pseudoallyl-4,4-dimethyl-1,3-
Figure BDA0000466800920000136
azoles quinoline-5-ketone; 2-vinyl-4-methyl-4-ethyl-1,3-
Figure BDA0000466800920000137
azoles quinoline-5-ketone; 2-pseudoallyl-3-oxa--1-azepine [4.5] spiral shell last of the ten Heavenly stems-1-alkene-4-ketone; 2-vinyl-5,6-dihydro-4H-1,3-
Figure BDA0000466800920000138
piperazine-6-ketone; 2-vinyl-4,5,6,7-tetrahydrochysene-1,3-oxygen azatropylidene-7-ketone; 2-pseudoallyl-5,6-dihydro-5,5-bis-(2-aminomethyl phenyl)-4H-1,3-
Figure BDA0000466800920000139
piperazine-6-ketone; 2-acryloxy-1,3- azoles quinoline-5-ketone; 2-(2-acryloxy) ethyl-4,4-dimethyl-1,3-
Figure BDA00004668009200001311
azoles quinoline-5-ketone; 2-vinyl-4,5-dihydro-6H-1,3-
Figure BDA00004668009200001312
piperazine-6-ketone; And 2-vinyl-4,5-dihydro-4,4-dimethyl-6H-1,3-
Figure BDA00004668009200001313
piperazine-6-ketone.
The representativeness of formula III a
Figure BDA00004668009200001314
the functional compound that azoles quinoline base replaces comprises: 2-vinyl-2-
Figure BDA00004668009200001315
azoles quinoline, 2-pseudoallyl-2-
Figure BDA00004668009200001316
azoles quinoline, 2-(5-hexenyl)-2-
Figure BDA00004668009200001317
azoles quinoline, 2-acryloxy-2- azoles quinoline, 2-(4-acryloxy phenyl)-2- azoles quinoline and 2-methacryloxy-2-
Figure BDA00004668009200001320
azoles beautiful jade.
The functional compound that the representative acetoacetyl of formula III replaces comprises 2-(acetoacetyl) ethyl propenoate.
The functional compound of the representative carboxyl substituted of formula III a comprises: (methyl) vinylformic acid, 3-(methyl) acryloxy-propionic acid, 4-(methyl) acryloxy-butyric acid, 2-(methyl) acryloxy-phenylformic acid, 3-(methyl) acryloxy-5-tolyl acid, 4-(methyl) acryloyl-oxy ylmethyl-phenylformic acid, phthalic acid list-[2-(methyl) acryloxy-ethyl] ester, tetrolic acid and 4-pentynoic acid.
The functional compound that the representative isocyanate groups of formula III a replaces comprises: (methyl) vinylformic acid (2-ethyl isocyanate, (methyl) vinylformic acid 3-propyl isocyanate, (methyl) vinylformic acid 4-NSC 87419,4-isocyanato vinylbenzene, 2-methyl-2-acryl isocyanic ester, 4-(2-(methyl) acryloxy ethoxy carbonyl is amino) phenyl isocyanate, allyl group 2-isocyanato ether and 3-isocyanato-1-propylene.
The functional compound that the representative epoxy group(ing) of formula III a replaces comprises: (methyl) glycidyl acrylate, (methyl) vinylformic acid sulfo-glycidyl ester, 3-(2,3-glycidoxy) phenyl (methyl) acrylate, 2-[4-(2,3-glycidoxy) phenyl]-2-(4-(methyl) acryloxy phenyl) propane, 4-(2,3-glycidoxy) cyclohexyl (methyl) acrylate, 2,3-epoxycyclohexyl (methyl) acrylate and 3,4-epoxycyclohexyl (methyl) acrylate.
The functional compound that the representative '-aziridino of formula III a replaces comprises: N-(methyl) acryloyl aziridine, 2-(1-'-aziridino) ethyl (methyl) acrylate, 4-(1-'-aziridino) butylacrylic acid ester, 2-[2-(1-'-aziridino) oxyethyl group] ethyl (methyl) acrylate, 2-[2-(1-'-aziridino) ethoxy carbonyl be amino] ethyl (methyl) acrylate, 12-[2-(2,2,3,3-tetramethyl--1-'-aziridino) ethoxy carbonyl is amino] dodecyl (methyl) acrylate and 1-(2-propenyl) aziridine.
The functional compound that the representative acid halide group of formula III a replaces comprises: (methyl) acrylate chloride, α-chlorine (methyl) acrylate chloride, (methyl) acryloxy Acetyl Chloride 98Min., 5-hexene acyl chlorides, 2-(acryloxy) propionyl chloride, 3-(acryloyl sulphur oxygen base) propionyl chloride and 3-(N-acryloyl-N-methylamino) propionyl chloride.
The functional monomer that representational anhydride group replaces comprises: maleic anhydride, (methyl) acrylic anhydride, itaconic anhydride, 3-(methyl) acryloxy Tetra hydro Phthalic anhydride and 2-(methyl) acryloxy cyclohexane dicarboxylic acid acid anhydrides.
The preferred ethylenically unsaturated compounds (" functionalized propylene's acyl compounds ") with reactive functional groups comprises: hydroxyalkyl acrylate, such as 2-hydroxyethyl (methyl) acrylate and 2-(2-hydroxyl-oxethyl) ethyl (methyl) acrylate; Aminoalkyl group (methyl) acrylate, such as 3-aminopropyl (methyl) acrylate and 4-amino-benzene ethene; azoles quinoline based compound is such as vinyl-1,3- azoles quinoline-5-ketone and 2-vinyl-4,4-dimethyl-1,3-
Figure BDA0000466800920000143
azoles quinoline-5-ketone; The compound of carboxyl substituted, such as (methyl) vinylformic acid and (methyl) vinylformic acid-4-carboxylic benzyl ester; The compound that isocyanato replaces, such as (methyl) vinylformic acid isocyanato ethyl ester and (methyl) vinylformic acid-4-isocyanato cyclohexyl; The compound that epoxy group(ing) replaces, such as (methyl) glycidyl acrylate; The compound that '-aziridino replaces, such as N-acryloyl aziridine and 1-(2-propenyl) aziridine; And acryloyl halide compound, such as (methyl) acrylate chloride.
About formula III b, described reactive group A 2optional from as above those.Y for its on the interactional surface-modifying groups of substrate (for example band backing, metallic surface, glass, glass cloth or Y group show any surface of avidity to it) (be physics or chemically interact, it for example can be covalency or ion) of curable composition is set.In certain embodiments, Y is that (P (O) (OH) for thiol group (SH), monophosphate base, phosphonic acid ester or phosphonate group 2), hydroxamic acid base (C (O) NHOH), carboxylic acid group (C (O) OH),-sulfinic acid or sulfonic group, phosphuret-(t)ed hydrogen base, alkyd resin basedly (comprise catechol and 1,2,3-trihydroxybenzene derivative), amine, isonitrile group, silyl, disulfide group (SS-) or heterocyclic aromatic group (for example benzotriazole base thiazolyl, benzimidazolyl-or pyridyl).
More preferably, Y is thiol group, monophosphate base, phosphonate group, carboxylic acid group, silyl base or benzotriazole base.For alumina surface, preferred Y comprises phosphonate group, and (P (O) (OH) 2), hydroxamic acid base (C (O) NHOH) or carboxylic acid group (C (O) OH).For ferric oxide or steel base, preferably Y comprises hydroxamic acid base (C (O) NHOH).For cupric oxide, preferably Y comprises hydroxamic acid base (C (O) NHOH), thiol group (SH), monophosphate base, phosphonic acid ester or phosphonate group, triazolyl base, thiazolyl base, benzimidazolyl-or pyridyl.For silicon oxide or glass, the silyl that preferably Y is following formula :-SiR 7 3, each R wherein 7group is independently selected from alkoxyl group, acetoxyl group and halogen ion.For gold, copper and silver, preferably Y is thiol group (SH) or disulfide group (S-S-).For platinum, preferably Y comprises pyridyl or phosphino-.
Also will understand, except simple ester group or amide group, the compound of formula II also can be provided with functional group other nucleophilic or parent's electricity.X referring to formula II 2group, it comprises the functional group of close electricity or nucleophilic, X 2can be selected from :-OH ,-Cl ,-Br ,-NR 4h ,-R 6-NCO ,-R 6-SH ,-R 6-OH ,-R 6-NR 4h ,-R 6-Si (OR 4) 3,-R 6-halogen ion ,-R 6-aziridine ,-R 6-epoxy group(ing) ,-R 6-N 3,-R 6-acid anhydrides ,-R 6-succinate ,-R 6-NR 4h and other parent's electricity or nucleophilic functional group.
Each R wherein 6for have 1 to 6 carbon atom alkylidene group, there are 5 or 6 yuan of cycloalkylidene groups of 5 to 10 carbon atoms, or there is the divalent aromatic radical of 6 to 16 carbon atoms.R 6can be replaced by one or more Lian Zhong functional group, described functional group comprises ether, amine, thioether, ester, acid amides, urea and carbamate-functional, for example R 6-NH-CO-O-R 6'-NCO, wherein R 6 'be defined as R 6.R 4for H or C 1-C 4alkyl.
As previously mentioned, R 1, R 2and R 3one or more groups " Y " that not only can comprise polymerisable group " Z " but also can comprise surface modification in group.The illustrative example of these embodiment comprises following structure A to E.Can be by making as follows by apparent this class formation: (methyl) acryloyl compound of formula II and epoxy functionalized (methyl) acrylate of formula III a are reacted such as glycidyl methacrylate; then for compd A to the hydroxyl of gained (from the ring-opening reaction of oxyethyl group) is functionalized with diacyl compound or cyclic acid anhydride for C, for Compound D POCl 3functionalized, hydrolysis subsequently, or with silyl functional isocyanic ester, come functionalized for compd E.
The present invention also provides the polymerisable compound for the preparation of (methyl) Voncoat R 3310 and multipolymer, addition-clastogen that described polymerisable compound comprises formula I and at least one polymerisable monomer, such as (methyl) acryloyl monomer, it comprises acrylate, acid amides and acid.In general, the consumption of addition-clastogen of formula I, in the total monomer of 100 weight parts, is 0.1 to 10 weight part, preferably 0.1 to 5 weight part.
Monomer (methyl) acrylate that (methyl) acrylate monomer that can be used for preparing (methyl) acrylic ester polymer is non-tertiary alcohol, described alcohol comprises 1 to 14 carbon atom and preferably comprises average 4 to 12 carbon atoms.
The example that is suitable as the monomer of (methyl) acrylate monomer comprises the ester of acrylic or methacrylic acid and non-tertiary alcohol, described non-tertiary alcohol is such as ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 2-ethyl-n-butyl alcohol, 3, 5, 5-trimethylammonium-1-hexanol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, isooctyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propyl enanthol, DODECANOL, 1-, 1-tridecyl alcohol, 1-tetradecanol, geraniol, dihydro-citronellol etc.In certain embodiments, preferred (methyl) acrylate monomer is the ester of (methyl) vinylformic acid and butanols or isooctyl alcohol or their combination, but the combination of two or more different (methyl) acrylate monomers is also suitable.In certain embodiments, preferred (methyl) acrylate monomer be (methyl) vinylformic acid and derived from the ester of the alcohol (such as sec-n-octyl alcohol, geraniol, dihydro-citronellol) of renewable source.
In certain embodiments, expectation (methyl) acrylate monomer comprises high T gmonomer, described monomer has at least 25 ℃, and the T of preferred at least 50 ℃ g.The example that can be used for the proper monomer in the present invention includes but not limited to tert-butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate, methacrylic acid stearyl ester, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, methylbenzene alkene acid benzyl ester, vinylformic acid 3, 3, 5 3-methyl cyclohexanol esters, cyclohexyl acrylate, N-octyl acrylamide and propyl methacrylate or combination.
By 100 parts of total monomer content for the preparation of polymkeric substance, (methyl) acrylate monomer is with 100 weight parts at the most, and preferably the amount of 85 to 99.5 weight parts exists.Preferably, by 100 parts of total monomer content, (methyl) acrylate monomer exists with the amount of 90 to 95 weight parts.When comprising high T gduring monomer, multipolymer can comprise 30 weight parts at the most, preferred (methyl) acrylate monomer component of 20 weight parts at the most.
Described polymkeric substance also can comprise acid functional monomer, and wherein acid functional group can be acid itself, and as carboxylic acid, or a part can be its salt, as alkali metal carboxylate.Available acid functional monomer includes but not limited to be selected from those of ethylenic unsaturated carboxylic acid, ethylenic unsaturated sulfonic acid, the unsaturated phosphonic acids of ethylenic and their mixture.The example of this compounds comprises those that are selected from vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, citraconic acid, toxilic acid, oleic acid, (methyl) β-acryloxypropionic acid, methacrylic acid 2-sulphur ethyl ester, styrene sulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, vinyl phosphonate and their mixture.
Due to its availability, the acid functional monomer of sour copolymers containing hydroxyl and carboxyl groups is generally selected from ethylenic unsaturated carboxylic acid, i.e. (methyl) vinylformic acid.When stronger sour of needs, acid monomer comprises ethylenic unsaturated sulfonic acid and the unsaturated phosphonic acids of ethylenic.Described acid functional monomer's consumption, in 100 weight part total monomers, is generally 0.5 weight part to 15 weight part, preferably 1 weight part to 15 weight part, most preferably 5 weight part to 10 weight parts.
Polymkeric substance also can comprise polar monomer.The polar monomer that can be used for preparing multipolymer is oil soluble and more or less water-soluble more or less, thereby causes polar monomer in letex polymerization, to be distributed between water and oil phase.As used herein, term " polar monomer " does not comprise acid functional monomer.
The representative example of suitable polar monomer includes but not limited to: (methyl) vinylformic acid 2-hydroxyl ethyl ester; NVP; N-caprolactam; Acrylamide; Single-or two-N-AAM; N-tert-butyl acrylamide; Dimethylaminoethyl acrylamide; N-octyl acrylamide; Poly-(alkoxyalkyl) (methyl) esters of acrylic acid, comprises (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-methoxy ethoxy ethyl ester, methacrylic acid 2-methoxyl group ethyl ester, polyethyleneglycol (methyl) acrylate; Alkyl vinyl ethers, comprises vinyl methyl ether; And their mixture.Preferred polar monomer comprises those that are selected from (methyl) vinylformic acid 2-hydroxyl ethyl ester and NVP.In 100 weight part total monomers, polar monomer can 0 to 10 weight part, and preferably the amount of 0.5 to 5 weight part exists.
Polymkeric substance also can comprise vinyl monomer.When using, the vinyl monomer that can be used for (methyl) acrylic ester polymer comprises vinylbenzene (for example alpha-methyl styrene), vinyl halide and their mixture of vinyl acetate (for example vinyl-acetic ester and propionate), vinylbenzene, replacement.As used herein, vinyl monomer does not comprise acid functional monomer, acrylate monomer and polar monomer.In 100 weight part total monomers, these vinyl monomers are generally with 0 to 5 weight part, and preferably 1 to 5 weight part is used.
In order to improve the cohesive strength of composition, multifunctional (methyl) acrylate can be mixed in the blend of polymerisable monomer.Polyfunctional acrylic ester especially can be used for emulsion or slurry polymerisation.The example of available multifunctional (methyl) acrylate includes but not limited to two (methyl) acrylate, three (methyl) acrylate and four (methyl) acrylate, such as 1,6-hexylene glycol two (methyl) acrylate, PEG two (methyl) acrylate, polyhutadiene two (methyl) acrylate, urethane two (methyl) acrylate and propoxylation three (methyl) vinylformic acid glyceryl ester and their mixture.The amount of multifunctional (methyl) acrylate and kind are according to the customization that should be used for of binder composition.Conventionally, in the gross dry weight of binder composition, multifunctional (methyl) acrylate exists to be less than the amount of 5 parts.More specifically, in 100 parts of total monomers of binder composition, linking agent can be with 0.01 to 5 part, and preferably the amount of 0.05 to 1 part exists.
In this type of embodiment, multipolymer can comprise:
I. 100 weight parts, preferably (methyl) acrylate of 85 to 99.5 weight parts at the most;
Ii.0 to 15 weight part, preferably sour official's energy ethylenically unsaturated monomers of 0.5 to 15 weight part;
Non-sour official's energy of iii.0 to 15 weight part, ethylenic unsaturated polar monomer;
The vinyl monomer of iv.0 to 5 part;
Multifunctional (methyl) acrylate of v.0 to 5 part;
The polymerizable photoinitiator of vi.0 to 5 part.
Below all by 100 weight part total monomers.
Composition can with thermal initiator or light trigger polymerization.The radical initiator of any routine all can be used for generating initial free radical.The example of suitable thermal initiator comprises superoxide, such as, benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, peroxidation hexanaphthene, methyl ethyl ketone peroxide, hydroperoxide are (for example, tert-butyl hydroperoxide and cumene hydroperoxide), dicyclohexyl peroxy dicarbonate, 2,2-azo-bis-(isopropyl cyanide) and t-butylperoxyl benzoate.The example of the thermal initiator of commercially available acquisition comprises the initiator purchased from special chemical article company of Delaware, USA Wilmington city Du Pont (DuPont Specialty Chemical (Wilmington, Del.)) with trade(brand)name VAZO, and it comprises VAZO tM67(2,2'--azo-bis-(2-methylbutyronitrile)), VAZO tM64(2,2'-azo-bis-(isopropyl cyanide)) and VAZO tM52(2,2'-azo-bis-(2,2-methyl pentane nitrile)), and with trade(brand)name Lucidol tMthe initiator of the 70 North America Ai Erfu atropic companies (Elf Atochem North America (Philadelphia, Pa)) purchased from Philadelphia, PA, USA.
Available light trigger comprises benzoin ether, such as benzoin methylether and benzoin iso-propylether; The methyl phenyl ketone replacing, such as 2,2-dimethoxy-acetophenone, (it is with trade(brand)name Irgacure tM651 light triggers are buied (Ciba company limited (Ciba Specialty Chemicals)), 2,2 dimethoxys-2-phenyl-l-methyl phenyl ketone (with trade(brand)name Esacure tMkB-1 light trigger is buied (western red this special Sartomer company of Pennsylvania, America (Sartomer Co., West Chester, PA)) and dimethoxy hydroxy acetophenone; The α-one alcohol replacing is such as 2-methyl-2-hydroxypropiophenonepreparation; Aromatics SULPHURYL CHLORIDE is as 2-naphthalic sulfonic chloride; And photosensitive oxime, as 1-phenyl-1,2-propanedione-2-(O-oxyethyl group-carbonyl) oxime.Especially preferred among these is the methyl phenyl ketone replacing.
Initiator to be effectively to promote free radical addition to use to the amount on addition-fracture linking agent, and described content amount will be according to for example initiator type, polymericular weight and required degree of functionalization and difference.The consumption of initiator, in 100 parts of total monomers, can be approximately 0.001 weight part to approximately 5 weight parts.
Curable compositions also can comprise other additive.The example of suitable additive comprises that tackifier (for example, rosin ester, terpenes, phenol, and the mixture of aliphatic series, the synthetic hydrocarbon resin of aromatics or aliphatic series and the synthetic hydrocarbon resin of aromatics), tensio-active agent, softening agent (not being pneumatogen), nucleator (for example, talcum, silicon-dioxide or TiO 2), pigment, dyestuff, toughener, solid packing, stablizer (for example, UV stablizer) and their combination.The addition of additive can be enough to obtain the desired character of prepared curing composition.Desired character is determined by the expection application of resulting polymers goods to a great extent.
In certain embodiments, crosslinkable composition can comprise filler.In certain embodiments, the total amount of filler is maximum 50 % by weight, preferred maximum 30 % by weight, and the more preferably filler of maximum 10 % by weight.Filler optional in multiple material as known in the art one or more, and comprise organic and mineral filler.Inorganic filler particle comprises the non-glass state particulate of type described in silicon-dioxide, zirconium white, sub-micron zirconium oxide and United States Patent (USP) 4,503,169 (Randklev).
Filler component comprises nanometer grade silica particle, nanosize metal oxide particle and their combination.Nano filling is also described in the people such as U.S.7,090,721(Craig), 7,090, the people such as 722(Budd), 7,156, the people such as 911(Kangas) and the people such as 7,649,029(Kolb) in.
In some preferred embodiments, curable compositions comprises nano particle and/or the nano-cluster with the bonding between reinforcing filler and monomer and/or polymkeric substance with the surface treatment of organo-metallic coupling agent.Organo-metallic coupling agent can, with reactive curing groups as acrylate, methacrylic ester, vinyl groups etc. carry out functionalizedly, and can comprise silane, zirconate or titanate coupling agent.
Suitable can have following general formula: CH by copolymerization organometallic compound 2=C (CH 3) msi (OR) nr 3-nor CH 2=C (CH 3) mc=OOR 21si (OR) nr 3-n; Wherein m be 0 or 1, R be the alkyl group with 1 to 4 carbon atom, R 21for the organic linking group of divalence, and n is 1 to 3.Preferred coupling agent comprises γ-methacryloxypropyl trimethoxy silane, γ-sulfydryl propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane etc.
Can be used for the multiple ordinary method of the surface modification of nano particle for example to comprise to nano particle and add the surface-modifying agent form of powder or colloidal dispersion (for example with), and allow surface-modifying agent to react with nano particle.Other available surface modifying method is described in for example United States Patent (USP) 2,801,185 (Iler), United States Patent (USP) 4,522, the people such as 958(Das), U.S.6, the people such as 586,483(Kolb) in, described document is all incorporated to herein separately by reference.
Surface-modifying groups can be derived from surface-modifying agent.Schematically, surface-modifying agent can represent by formula A-B, and wherein can be attached to surface (being the silanol of silica dioxide granule) and the B group of particle be reactive or non-reacted functional group to A group.Non-functional group be not with system (for example substrate) in the group of other component reaction.Can select non-reacted functional group so that particle has relatively more polarity, polarity relatively still less or relatively nonpolar.In certain embodiments, non-reacted functional group " B " is hydrophilic radical, such as acid groups (comprising carboxylate radical, sulfonate radical and phosphonate groups), ammonium group or poly-(oxygen ethene) group or oh group.In other embodiments, " B " can be reactive functional groups as ethylenic unsaturated polymerizable group, comprise vinyl, allyl group, vinyloxy group, allyloxy and (methyl) acryloyl, described group can with polymerizable resin or monomer radical polymerization.
The surface-modifying agent of examples of such optional can a certain amount ofly be used, and makes 0 to 100%, if 1 to 90%(existed in general) the surface functional group (Si-OH group) of nano SiO 2 particle functionalised.With experimental technique, determine the number of functional group, wherein make a large amount of nano particles react with excessive surface-modifying agent, make all available reactive sites all functionalized by surface-modifying agent.Then can be calculated by result the lower limit of functionalized per-cent.In general, the consumption of surface-modifying agent is enough to provide with respect to the inorganic nanoparticles weight surface-modifying agent of equivalent weight twice at the most.When using, the weight ratio of surface-modifying agent and inorganic nanoparticles is preferably 2:1 to 1:10.If expectation surface modification nano SiO 2 particle, preferably before mixing coating composition by modified by nano particles.
In some preferred embodiments, filler is silica filler especially, addition-clastogen surface modification of available formula I.Thereby the disclosure provides, addition-monomer modified filler particles ruptures.As described herein, the filler particles of these surface modifications can and solidify with the compounding of polymerizable thing mixture, and result is integrated into filler particles in curing composition.Combined type I, the granular filler of surface modification can be as follows:
Figure BDA0000466800920000221
Wherein
Filler is inorganic filler particle,
R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y ' is the residue of described surface modification organo-functional group, and the substrate that described addition-clastogen is set on itself and its is associated;
M is 1 to 6;
P is 1 or 2;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
Should be appreciated that in above formula, by the R of formula I 1group is chosen to " Y-Q '-" surface-modifying groups, and can illustration R 1, R 2and/or R 3in any.It is also understood that R 1, R 2and R 3in each comprised Z m-Q-and Y p-Q '-group both, polymerizable groups and surface-modifying groups are a part for identical " R " group.
As used herein, term " residue " is for limiting the part of the functional group of the surface reaction that maintains functional group and inorganic particle, for example, and formula-SiR 7 3" residue " of silane functional Y will be-O-Si (R 7) 2-.
For other illustrating, specific filler can be selected from silicon-dioxide (or silicon dioxide composite material), and surface modification organo-functional group " Y " can be selected from formula-SiR 7 3silyl-group, each R wherein 7group is independently selected from alkoxyl group, acetoxyl group and halogen ion.This will cause (the R by silicon-dioxide-O-Si 7) 2covalent linkage between the illustrative silica dioxide granule of-key and addition clastogen.Should be appreciated that silyl part can form one (as illustrated in) or a plurality of siloxane bond with silica dioxide granule, or form siloxane bond with oxygen methyl-silicane base group.Referring to formula I, can select Y=hydroxamic acid or N-hydroxyurea, it is bonding, and to zirconium white, for the filler of high refractive index coating/film and dental composite, Y=phosphoric acid ester and phosphonic acid ester will also can be used in alumina packing, and Y=is for golden mercaptan.
In general, addition-clastogen modification like this that all or part of surface functional group of inorganic filler particle also can through type I.Filler can be unmodified, and the mixture of those of the surface-modifying agent by conventional surface-modifying agent, formula I or conventional surface-modifying agent and formula I carries out surface modification.Preferably, with respect to the weight of the weight of filler particles, addition-clastogen is used with the amount of 0.5 % by weight to 10 % by weight.
Surface modification can be carried out or carry out after mixing following closely after mixing with polymerisable monomer.Conventionally preferably by organosilane surface treatment compound and nano particle combination, then mix in resin.The aequum of surface-modifying agent depends on many factors, for example the molecular weight of granularity, grain type, properties-correcting agent and properties-correcting agent type.In general, preferably the properties-correcting agent of about individual layer is attached to the surface of particle.
Addition clastogen of the present invention also can be used for preparing hard coat.Term " hard coat " or " hard coat " refer to layer or the coating on the outside surface that is positioned at object, wherein become at least to make object to avoid abrasion on described layer or coated designs.The disclosure provides hard coating composition, and described composition comprises: addition-clastogen of formula I and comprise three or more (methyl) acrylate-based multifunctional (methyl) acrylate monomer and/or multifunctional (methyl) origoester acrylate and (methyl) acrylate-functional thinner optionally.
It is acrylate-based that available multifunctional (methyl) acrylate monomer comprises three or more (methyl); Multifunctional (methyl) acrylate monomer can be used for practice of the present invention, because it has increased the wear resistance of hard coat.Comprise three or more (methyl) acrylate-based preferably multifunctional (methyl) acrylate monomers and comprise trimethylolpropane tris (methyl) acrylate (TMPTA), three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, two (trishydroxymethyl) propane esters (Sartomer355) of three (methyl) vinylformic acid, five (methyl) vinylformic acid dipentaerythritol ester (Sartomer399), hydroxyl five (methyl) vinylformic acid dipentaerythritol ester (DPHPA), propoxy-three (methyl) vinylformic acid glyceryl ester, three (methyl) vinylformic acid trihydroxymethylpropanyl ester and their mixture.The component of the radiation-hardenable of the present invention that another is available is for having two or more (methyl) acrylate groups, and molecular-weight average (Mw) multifunctional (methyl) origoester acrylate in approximately 400 to 2000 scopes.
Available multifunctional (methyl) origoester acrylate comprises polyester (methyl) acrylate, urethane (methyl) acrylate and (methyl) acroleic acid esterification epoxy (methyl) acrylate.Most preferably therefore (methyl) acroleic acid esterification epoxy (methyl) acrylate and polyester (methyl) acrylate, because it is tending towards having relatively low viscosity, and allow to apply more uniform coating by spin coating method.Particularly, preferably comprise can be from (the UCB Radcure of UCB Radcure company limited in Shi Maina city, Georgia for multifunctional (methyl) origoester acrylate, Inc.of Smyrna, Georgia) commercially available and with trade(brand)name Ebecryl (Eb), sell those: Eb4O(tetra-functional acrylic esterification polyester oligomers), ENO(polyester four senses (methyl) origoester acrylate), Eb8I(multifunctional (methyl) acrylated polyester oligomer), Eb6OO(bisphenol-A epoxy two (methyl) acrylate), bisphenol-A epoxy two (methyl) acrylate of 25% 2 (methyl) vinylformic acid tripropylene glycol ester dilution for Eb6O5(), Eb639(phenolic aldehyde polyester oligomer), the polyester oligomer of Eb2O47(trifunctional acroleic acid esterification), Eb3500(bis-sense dihydroxyphenyl propane oligopolymer acrylate), Eb3604(polyfunctional poly ester oligomer acrylate), Eb6602(trifunctional aromatic urethanes origoester acrylate), Eb8301(six sense aliphatic urethane acrylate), EbW2(difunctionality aliphatic urethane origoester acrylate), and their mixture.Wherein, most preferably Eb600, Eb6O5, Eb80 and Eb8l.
(methyl) acrylate-functional thinner, herein also referred to as " reactive diluent ", is relatively low-molecular-weight simple function or dual functional non-aromatic (methyl) acrylate monomer.These relatively low-molecular-weight reactive diluents are favourable for be for example less than the relative low viscosity of approximately 30 centipoises (cps) under 25C.Dual functional non-aromatic (methyl) acrylate is generally preferred than simple function non-aromatic (methyl) acrylate, because dual functional non-aromatic (methyl) acrylate allows set time faster.Preferred reactive diluent comprises two (methyl) vinylformic acid 1, 6-hexylene glycol ester (derives from (the UCB Radcure of UCB Radcure company limited in Shi Maina city, Georgia, Inc.of Smyrna, Georgia) HDODA), two (methyl) vinylformic acid tripropylene glycol ester, (methyl) isobornyl acrylate (1130A, Radcure company (Radcure)), (methyl) acrylate 2 (2-ethoxy ethoxy) ethyl ester is (with trade(brand)name Sartomer256 by pause (the SARTOMER Company of Sartomer company in city of Pennsylvania's Aix-en-Provence, Inc.of Exton, Pennsylvania) sell), N-vinyl formamide (Sartomer497), (methyl) tetrahydrofurfuryl acrylate (Sartomer285), two (methyl) polyalkylene glycol acrylate ester (Sartomer344), two (methyl) vinylformic acid tripropylene glycol ester (Radcure company (Radcure)), two (methyl) vinylformic acid neopentyl glycol dialkoxy ester, two (methyl) polyalkylene glycol acrylate ester, and their mixture.
Described hard coating composition can comprise:
(silicon-dioxide of the AFM of 0.1-10 % by weight and/or AFM-modification, whether weight percent is with reference to AFM itself, no matter as functionalized filler (0.1-10 % by weight AFM)
Multifunctional (methyl) acrylate monomer of 20-75 % by weight and/or multifunctional (methyl) origoester acrylate,
(methyl) acrylate thinner within the scope of 0 % by weight to 25 % by weight, (0-25 % by weight)
The silicon-dioxide of 20 to 75 % by weight.(20-75 % by weight), whether weight range is with reference to silicon-dioxide itself, no matter functionalized.
In certain embodiments, comprise AFM surface modification silicon-dioxide, by the amount of the silicon-dioxide of conventional surface-modifying agent modification and the silicon-dioxide of unmodified silicon-dioxide, be 20-75 % by weight, preferably 50-70 % by weight.
Addition clastogen also can be used for preparing dental composition, as described in the applicant's who is entitled as " Dental Compositions Comprising Addition-Fragmentation Agent " (dental composition that comprises addition-clastogen) who submits on August 23rd, 2011 patent application U.S.S.N61/526437 common co-pending, described patent application is incorporated to way of reference in full.
example
Except as otherwise noted, all per-cent and ratio are all by weight.
testing method
wo Ci shrinks testing method
Wo Ci shrinks the contraction that (Watts) testing method is measured test sample composition by the stereomutation after solidifying.Described in below with reference to document, carry out sample preparation (the uncured test sample composition of 90mg) and test procedure: the polymerization shrinkage in Determination of Polymerization Shrinkage Kinetics in Visible-Light-Cured Materials:Methods Development(visible light solidifying material is dynamic (dynamical) definite: method exploitation), Dental Materials < < dental material > >, in October, 1991, the 281st to 286 pages.Report the test is negative contraction %.
radial drawing strength (DTS) testing method
In this test, measure the Radial drawing strength of curing composition.Uncured test sample composition is injected to 4mm(internal diameter) Glass tubing; And with sillicon rubber blocking by described pipe end-blocking.With about 2.88kg/cm 2pressure will manage axial compression 5 minutes.Then by being exposed to XL1500 dentistry cure lamp ((the 3M ESPE of 3M company of Sao Paulo City, the Minnesota State, St.Paul, MN)) make sample photocuring 80 seconds, at Kulzer UniXS, solidify in case (Germany congratulates Li Shi Gu Sha company limited (Heraeus Kulzer GmbH, Germany)) and irradiate 90 seconds subsequently.Use diamond saw cutting test sample to form the dish that about 2mm is thick, before test, it is stored at 37 ℃ in distilled water to approximately 24 hours.Measurement is at Instron test machine (Instron4505, (the Instron Corp. of Instron company of Massachusetts, United States Canton, Canton, MA)) upper with 10,000 Ns of (kN) load sensors with the chuck speed of 1mm/ minute according to ISO specification 7489(or the specification No.27 of ADA (ADA)) implement.The mean value report of test result repeatedly to measure, in MPa(MPa).
stress test method
Stress test method is measured stress development during the solidification process of test sample composition.In the aluminium block of rectangle 15 * 8 * 8mm, mechanical workout goes out 8 * 2.5 * 2mm slit to be formed for the test fixture of each test sample.Described slit is positioned at along 2mm place, edge, thereby it is most advanced and sophisticated to have formed the wide aluminium of the 2mm adjacent and parallel with the wide cavity of the 2mm that holds composition to be tested.Linear variable displacement transducer (GT1000 type is set, use together with E309 analogue amplifier, both all derive from (the RDP Electronics of RDP electronics corporation of Britain, United Kingdom)), so that along with the displacement that at room temperature Photosetting is measured described tip end of described composition.Before test, slit in aluminium block is used Rocatec Plus special surface coating sand-blast material ((the 3M ESPE of 3M company of Sao Paulo City, the Minnesota State, St.Paul, MN)) sandblast, with RelyX pottery priming paint (3M ESPE), process, and finally use dental cement Adper Easy Bond (3M ESPE) to process.Slit fills up with about 100mg sample composition.Dentistry cure lamp (Elipar S-10 for described material, 3M ESPE) irradiate 1 minute, described dentistry cure lamp is positioned to almost contact with the material in (<1mm) slit, then within 9 minutes after lamp extinguishes, records most advanced and sophisticated displacement (in micron).
curing depth testing method
Measure the curing depth (DOC) of the test sample composition after solidifying.The test fixture with 8 millimeters of stainless steel mould cavitys of opening is placed on polyester film and with sample composition and is filled.The second polyester film is placed in to the top of resin extrusion clamp so that horizontal surface to be provided on composition.The test fixture of filling is placed on white background surface, and use dentistry cure lamp (3M dental product cure lamp 2500 or 3M ESPE Elipar FreeLight2, all by 3M ESPE dental product company (3M ESPE Dental Products) preparation) to irradiate composition 20 seconds.After solidifying, from mould, remove sample and remove gently uncured resin, for example, swiping gently from the material of sample bottom (it is the non-irradiated side of cure lamp).Measure the thickness of residue curing material.The degree of depth of reporting be actual cured thickness divided by 2(in millimeter).
overlapping shearing test
Use is measured as the aluminum test sample piece of 1 * 4 * 1/16 inch (2.54 * 10.2 * 0.159cm) and tests overlapping shearing resistance.With grinding pad (the heavy scouring pad of Scotch-Brite, (the 3M Company of 3M company of Saint Paul City, State of Minnesota, US; St.Paul, MN, USA)) bonding surface of the coupon of about 2.54cm that swipes.Then by methyl ethyl ketone (MEK) is sprayed on the coupon on paper handkerchief, and with paper handkerchief, wipe MEK and clean coupon.For each test adhesive sample, prepare three coupons.
By binder composition being mixed and 4 adhesive gasket being assigned on scraping region and making adhesive coverage 2.54 * 1.27cm region prepare tackiness agent test sample.By the spacer beads of 3-5 mil (0.0762-0.127mm) diameter (VI class soda-lime glass ball, (the MO-SCI Specialty Products of MO-SCI Special Products company in Missouri, USA roller city; Rolla, MO, USA)) be sprinkled upon on adhesive surface.The second coupon is placed on tackiness agent, and making tackiness agent overlapping is 2.54cm * 1.27cm * 0.127mm, and the free end of coupon extends in an opposite direction.Binder clip is placed on the lap of coupon, and the second binder clip is placed on the other end of coupon.Make tackiness agent test sample at room temperature solidify 5-7 days.
Speed with 0.1 inch per minute clock is tested in the tensile test device with 5625lb load sensor.Power (in pound per square inch) when record lost efficacy, and with MPa (MPa) report.Tensile test device can trade name Insight30MTS or Sintech5/GL MTS Systm Corp. (MTS Systems Corporation, Eden Prairie, MN, USA) that she steps on Prey from Minn. buy.
adhesive treatment test
The processing of binder composition is the degree of wetting in matrix by tackiness agent, and working life, and tackiness agent can be worked and how long evaluated in gelling and before solidifying.Tackiness agent test sample is by embarking on journey 12 points (approximately 1.8cm diameter) tackiness agent to be distributed on 8 * 2 inches of (20.3 * 5.08cm) high density polyethylene(HDPE)s (HDPE) coupon and prepare.Spacer beads (referring to overlapping shearing test) is spread across on the whole adhesive surface of each point, and the cover glass of microslide is pressed in downwards on front 2 points and opens stopwatch simultaneously.After 5 minutes, cover glass is pressed onto on contiguous point.Continue this process until all points are all capped.Wetting time is reported as the fully wetting cover glass of tackiness agent wherein to produce the final time of bonding, in minute, for example, if the edge of tackiness agent wetting cover glass when 10 minutes rather than 15 minutes, wetting time is reported as 10 minutes.
By start to reverse gently with the wooden rod that applies the working life that cover glass is evaluated every kind of tackiness agent with the interval of a minute at the past 2 points.Working life is reported as the time when cover glass no longer can be moved by rod.
the test of tackiness agent solidification internal stress
Construction adhesive is evaluated by measuring the distortion of curing rear tackiness agent on aluminium backing at the solidification internal stress experiencing between polymerization period.Stress in the larger indication cure adhesive of curling measurement is larger.Test procedure and equipment describe are in the U.S. Patent application 13/169306 of submitting on February 11st, 2012.
material-commercial reagents provides to use as supplier
The U.S. TCI company (TCI America, Portland, OR, USA) in 1,2-epoxy-3-phenoxypropane-Ore. Portland city
1,2--epoxy decane-the derive from U.S. TCI company (TCI America, Portland, OR, USA) in Ore. Portland city
The U.S. TCI company (TCI America, Portland, OR, USA) in methacrylic acid 2-isocyano-ethyl ester-Ore. Portland city
The A Faaisha company in Xi Er city, 2,6 di tert butyl 4 methyl phenol-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
2-[(methylsulfonyl) oxygen ethyl] 2-methacrylic ester-by M.J.Benes and J.Peska is at Collect.Czech.Chem.Commun., the program preparation of reporting in 1983,48,3065-3070
The Sigma aldrich company (Sigma Aldrich, St.Louis, MO, USA) in 3-isocyanato propyl-triethoxysilicane-St. Louis city
3-sulfydryl propyl-triethoxysilicane-A Faaisha company (Alfa Aesar)
3-sulfydryl propyl trimethoxy silicane-A Faaisha company (Alfa Aesar)
The A Faaisha company in Xi Er city, 4-(dimethylamino) pyridine-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
Nippon Kasei Chemical Company of vinylformic acid 4-hydroxyl butylglycidyl ether-Tokyo (Nippon Kasei Chemical, Tokyo, Japan)
The aldrich chemical company (Aldrich, Milwaukee, WI) of Milwaukee, 4-vinyl benzyl muriate-state of Wisconsin
The Sigma aldrich company (Sigma Aldrich, St.Louis, MO, USA) in acrylate chloride-St. Louis city
The Degussa company limited (Degussa Corporation, Piscataway, NJ, USA) in Aerosil200 silicon-dioxide-New Jersey Piscataway city
Solution of ammonium hydroxide-30% solution-Sigma aldrich company (Sigma Aldrich)
Benzotriazole-Sigma aldrich company (Sigma Aldrich)
BHT-Yoshinox BHT, the Sigma aldrich company (Sigma-Aldrich, Milwaukee, WI, USA) of Wisconsin, USA Milwaukee
Bis-EMA-6-Sartomer CD541(ethoxylation (6 moles of ethylene oxide) bisphenol a dimethacrylate, (the Union Carbide of Union Carbide Corporation in Piscataway city, New Jersey; Piscataway, NJ)
BisGMA-(2, two [4-(the 2-hydroxy-3-methyl acryloxy-propoxy-) phenyl] propane of 2-, Sigma aldrich company (Sigma Aldrich)
The A Faaisha company (Alfa Aesar, Heysham, Lanc, England) of the blue thatch Heysham of caprolactone-Britain
The EMD chemical company in gibbs city, dithiocarbonic anhydride-New Jersey (EMD Chemicals, Gibbstown, NJ)
CPQ-camphorquinone, Sigma aldrich company (Sigma-Alrich)
The A Faaisha company in Xi Er city, dibutyl tin laurate-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
The EMD chemical company in methylene dichloride-New Jersey gibbs city (EMD Chemicals, Gibbstown, NJ, USA)
DPIHFP-diphenyl iodine hexafluorophosphate (>=98%), Sigma aldrich company (Sigma-Alrich)
DMAEMA-2-N, N-dimethylaminoethyl methacrylic ester, Sigma aldrich company (Sigma-Alrich)
DMAP-4-N, N-dimethyl aminopyridine, the A Faaisha company in Xi Er city, Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
The curable acrylic resin of DP807 tackiness agent-2-part; 3M Scotch-Weld tMacryloid cement resin DP807Duo-pak, (the 3M Company of 3M company of Sao Paulo City, the Minnesota State; St.Paul, MN)
EDMAB-4-N, N-dimethylaminobenzoic acid ethyl ester, Sigma aldrich company (Sigma-Alrich)
ENMP-N-methyl-N-phenyl-3-alanine ethyl ester light trigger, CAS 2003-76-1; This is the compound of U.S. Patent application 2010-0311858 (Holmes) Chinese style 1-a, and described compound can pass through as people such as Adamson, JCSOA9; J.Chem.Soc. the magazine > of < < Chemical Society >; 1994, the 144th volume, the method described in 152 pages is synthetic, and it is incorporated to herein by reference.
The Pharmaco-AAPER company of ethanol-Connecticut, USA Brookfield (Pharmaco-AAPER, Brookfield, CT, USA)
The EMD chemical company in ethyl acetate-New Jersey gibbs city (EMDChemicals Inc., Gibbstown, NJ, USA)
GF-31 silane (3-methacryloxypropyl trimethoxy silane, the Wacker Chemical Co., Ltd of Munich, Germany (Wacker Chemie AG, Munich, Germany)
The A Faaisha company in Xi Er city, Pyroglutaric acid-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
The Pohle Sai Si company limited (Polysciences Inc., Warrington, PA, USA) of glycidyl acrylate-Pennsylvania, America Warrington
The A Faaisha company in Xi Er city, glycidyl methacrylate-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
HEMA-hydroxyethyl methylacrylate, Sigma aldrich company (Sigma-Aldrich)
Irgacure tM651 light triggers, derive from Ciba company limited (Ciba Specialty Chemicals).
Irgacure tMthe BASF Co., Ltd of 819 light triggers-Ludwigshafen, Germany (BASF Corporation, Ludwigshafen, Germany)
Lucirin TPO(2,4,6-trimethylbenzoyl diphenyl phosphine oxide, the Pohle Sai Si company limited (Polysciences, Inc, Warrington, PA, USA) of Pennsylvania, America Warrington
The avocado research Chemical Co., Ltd. (Avocado Research Chemicals, Ltd., Lancashire, England) of maleic anhydride-Lancashire United Kingdom
The A Faaisha company in Xi Er city, the chloro-Massachusetts, United States of methacryloyl Ward (Alfa Aesar, Ward Hill, MA, USA)
Methoxypropanol-Jie Supreme Being Bei Ke (Mallinkrodt) company (J.T.Baker (Mallinkrodt))
Methylene dichloride-Sigma aldrich company (Sigma-Aldrich)
The preparation of the own ester of MHP-phosphoric acid 6-methyl-prop methanoyl-compound is described in U.S. Patent application 2009-0011388(Craig, waits people) in.
The nano silicon methoxypropanol of Nalco2329k-41.33 % by weight 20 nanometers; (the Nalco Company of Ondeo Nalco Co. in Naperville city, Illinois; Naperville, IL)
Nanozirconia fillers-through the nano zirconium oxide powder of silane treatment, as United States Patent (USP) 7,156,911, is prepared described in preparation example 1A, and different is to use SILQUEST A-174 silane to replace SILQUEST A-1230.SILQUEST A-174 loads with about 1.2mmol silane/g oxide compound.
Nano silicon filler (also referred to as 20nm silicon-dioxide)-through the nano grade silica particles of silane treatment, it has the nominal particle size of 20nm; As United States Patent (USP) 6,572,693(the 21st hurdle, 63-67 is capable of nano-scale particle filler, type #2) described in prepare
Particle A(85m 2the cluster of particle material of/g silicon-dioxide/zirconium white nano-cluster)-gathering, general as United States Patent (USP) 6,730,156, described in preparation example A, prepare.Described material has 85m 2the surface-area of/g, and silicon-dioxide/zirconium white weight ratio of 73/27.The preparation of material is more specifically described in the U.S. Patent application 20110196062 of submitting on October 9th, 2009, Fillers and Composite Materials with Zirconia and Silica Nanoparticles(filler and and the composite substance with zirconium white and nano SiO 2 particle), (Bradley), in [0067]-[0073] section and reference wherein, (be filed in the United States Patent (USP) 6 on October 28th, 1999, 376, the people such as 590(Kolb), or be filed in the United States Patent (USP) 7 on June 7th, 2007, 429, the people such as 422(Davidson)), each in described reference is all incorporated to way of reference accordingly.
Particle B(125m 2/ g silicon-dioxide/zirconium white nano-cluster)-aggregate powdered material is prepared in the mode identical with particle A, and different is that particle has 125m 2the surface-area of/g.Particle ratio counts 73/27 by silicon-dioxide/zirconic weight.
PEG600DMA-PEGDMA-400 (CAS 25852-47-5), Sigma aldrich company (Sigma Aldrich)
Pentaerythritol triacrylate derives from Pennsylvania's Aix-en-Provence pause Sartomer U.S. company limited (Sartomer USA, the LLC in city; Exton, PA)
The EMD chemical company in sherwood oil-New Jersey gibbs city (EMD Chemicals Inc., Gibbstown, NJ, USA)
Vanadium Pentoxide in FLAKES (P 4o 10the A Faaisha company in Xi Er city)-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
Prostab-hydroxyl TEMPO, (the Sigma Aldrich of Sigma aldrich company in St. Louis city; St.Louis, MO USA)
The A Faaisha company (Alfa Aesar, Heysham, Lanc, England) of the blue thatch Heysham of pyridine-Britain
The Momentive of SILQUEST A-174 silane-New York, United States Albany tMperformance materials (Momentive tMperformance Materials, Albany, NY, USA)
Dispersion in sodium hydride-60% oil, the A Faaisha company in Xi Er city, Ward, Massachusetts (Alfa Aesar, Ward Hill, MA)
The A Faaisha company in Xi Er city, succinyl oxide-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
TEGDMA-dimethacrylate triethyleneglycol ester, the TCI u s company in Ore. Portland city (TCI America, Portland, OR, USA)
The EMD chemical company in tetrahydrofuran (THF)-New Jersey gibbs city (EMD Chemicals, Gibbstown, NJ, USA)
The A Faaisha company (Alfa Aesar, Heysham, Lanc, England) of the blue thatch Heysham of stannous octoate (II)-Britain
The EMD chemical company in toluene-New Jersey gibbs city (EMD Chemicals, Gibbstown, NJ, USA)
The Sigma aldrich company (Sigma Aldrich, St.Louis, MO, USA) in triethylamine-St. Louis city
The TCI company (TCI, Portland, OR, USA) in the chloro-Ore. Portland of trimellitic acid acid anhydrides city
The Sigma aldrich company (Sigma Aldrich, St.Louis, MO, USA) in antimony triphenyl-St. Louis city
The A Faaisha company in Xi Er city, triphenylphosphine-Massachusetts, United States Ward (Alfa Aesar, Ward Hill, MA, USA)
UDMA-Rohamere tM6661-0(dimethacrylate two urethane esters, CAS 41137-60-4), the Luo Men Science and Technology Ltd. in Morton city, Massachusetts (Rohm Tech, Inc., Malden, MA)
The reaction product of the multipolymer of VBCP-vinylformic acid and methylene-succinic acid and methacrylic acid 2-isocyanato ethyl ester, as United States Patent (USP) 5,130, preparation described in 347.
Z250-Filtek tMgeneral renovation agent-the 3M of Z250 ESPE
Instrument-use nucleus magnetic resonance photometer (UltraShield tMplus400MHz nucleus magnetic resonance photometer; (the Bruker Corporation of Brooker company in Bill Li Ka city, Zhu Sai state, Marseille; Billerica, MA) analysis NMR (Nuclear Magnetic Resonance) spectrum (proton-1H NMR; Carbon-13C; Phosphorus-31 P NMR) and record.
the distillation of methyl methacrylate oligomer mixture
Figure BDA0000466800920000351
Methyl methacrylate oligomer mixture is according to United States Patent (USP) 4,547, prepared by the program in 323 (Carlson, G.M.) described in example 1.Mixture is as Moad, C.L.; Moad, G.; Rizzardo, E.; And Thang, S.H.Macromolecules < < macromole > >, 1996, the 29th volume, distilled described in 7717-7726 page, and wherein details is as follows:
The methyl methacrylate oligomer mixture that packs 500g in the round-bottomed flask of 1L that is equipped with magnetic stirring bar into.Flask is furnished with Vigreaux column, condenser, distribution adapter and four collection flasks.By described water distilling apparatus be at room temperature placed under decompression (0.25mm Hg) continuously stirring until gas is overflowed (methyl methacrylate monomer is removed in indication) greatly weaken.Subsequently flask is heated in oil bath reflux with distillation oligomer mixture.Level by this program separation is respectively in table 1.
table 1-derives from the fraction of methyl methacrylate oligomer mixture distillation
Figure BDA0000466800920000361
the dimeric hydrolysis of methyl methacrylate
Figure BDA0000466800920000362
Dimer from fraction B is hydrolyzed into diacid 1 as Hutson, L.; Krstina, J.; Moad, G.; Morrow, G.R.; Postma, A.; Rizzardo, E.; And Thang, S.H.Macromolecules < < macromole > >, 2004, the 37th volume, described in 4441-4452 page, wherein details is as follows:
In being equipped with the 1L round-bottomed flask of magnetic stirring bar, pack deionized water (240mL) and potassium hydroxide (60.0g, 1007mmol) into.Stir the mixture until evenly.Add the methyl methacrylate dimer (75.0g, 374.6mmol) from fraction B.The flask that is equipped with reflux exchanger is heated to 90 ℃ in oil bath.After 17 hours, flask is removed from oil bath and allowed it to be cooled to room temperature.By adding dense HCl described reaction soln to be acidified to about 1 pH.During acidifying, form white precipitate.Heterogeneous mixture vacuum filtration is also used to the quick washed twice of deionized water of 50-100mL.By pulling air to pass solid, within about 4 hours, be dried white solid.Then described white solid is dissolved in the methylene dichloride of about 1750mL.The solid that is less than 1 gram keeps insoluble.Permission solution left standstill 24 hours and then vacuum filtration are to remove insoluble white solid.The dichloromethane solution of filtration is concentrated so that white solid to be provided in a vacuum.Under high vacuum, further dry described solid is to be provided as the diacid 1(55.95g of white powder, 325.0mmol, 87%).
the preparation of AFM-1
Figure BDA0000466800920000363
In being equipped with about 250mL amber bottle of magnetic stirring bar, pack glycidyl methacrylate (23.0mL, 24.8g, 174mmol) and antimony triphenyl (0.369g, 1.04mmol) into.With plastic cover, cover described bottle, two No. 16 needle pierces top covers being retained in lid wherein, it allows air to enter reaction.When stirring, mixture is heated in oil bath to 100 ℃.Through the times of 1.5 hours by diacid 1(15.0g, 87.1mmol) with aliquot, add in described reaction.After 21 hours, add triphenylphosphine (0.091g, 0.35mmol).At 100 ℃, stir described reaction other 6.5 hours.Analysis is from the sample of the reaction mixture at this some place, and the structure of the 1H NMR Analysis deterrmination AFM-1 mixture that is isomer, and indicated the consumption of glycidyl methacrylate.Reaction is cooled to room temperature so that AFM-1 to be provided, and it is the extremely flaxen thick substances of clarification.
the preparation of example 1-AFM-glutarate
Figure BDA0000466800920000371
In being equipped with about 25mL amber bottle of magnetic stirring bar, pack AFM-1(5.00g, 10.95mmol into) and Pyroglutaric acid (2.50g, 21.91mmol).Described bottle be coated with a slice have three apertures aluminium foil so that reaction be vented in air.Under agitation reaction is heated to 100 ℃.After 25.25 hours, reaction is cooled to room temperature sampling.According to 1h NMR analyzes, residual a small amount of pentanedioic acid.Under agitation will react and heat back 100 ℃.After other 24 hours, reaction is cooled to room temperature. 1the mixture that H NMR analysis confirmation AFM-glutarate structure is isomer.Obtain AFM-glutarate (7.39g, 10.8mmol, 99%), it is unusual thickness, extremely faint yellow oil.
the preparation of example 2-AFM-phosphoric acid ester
In being equipped with the glass jar of magnetic stirring bar, Vanadium Pentoxide in FLAKES (2.06g, 0.00725mol) is suspended in methylene dichloride.Add AFM-1(6.6g, 0.0144mol) and at room temperature mixture is stirred 4 hours.Then add water (0.25g, 0.014mol), and the mixture clarification that becomes, at the place, bottom of wide-necked bottle, leave separated a small amount of undissolved resistates.Continue to stir 3 hours, and then make mixture stay at room temperature to spend the night without interruption.The clarification of mixture on top is partly decanted in round-bottomed flask, in rotatory evaporator, removes subsequently desolventizing so that the light yellow viscous liquid of clarification to be provided.The yield of reaction is 85%.By 1H and 31P NMR, confirmed the structure of product.
the preparation of example 3-AFM-succinate
Figure BDA0000466800920000382
In the 50mL round-bottomed flask that is equipped with magnetic stirring bar and dry air blanket, pack AFM-1(5.95g, 0.013mol into), succinyl oxide (2.55g, o.255mol) DMAP(80mg) BHT(8mg).Under continuously stirring, in oil bath, at 95-100 ℃, flask is heated 5 hours.Close and heat and collect product, it has 100% yield substantially, is the light yellow liquid of clarification.By 1H and 13C NMR, confirm the structure of AFM-succinate.
the preparation of example 4-AFM-maleic acid ester
Figure BDA0000466800920000391
AFM-maleic acid ester is for the similar program of preparation AFM-succinate, by AFM-1(6.6g, 0.0145mol) and maleic anhydride (avocado of Lancashire United Kingdom is studied Chemical Co., Ltd.) (2.8g, 0.028mol) prepare.The yield of reaction is essentially 100%.AFM-maleic acid ester is separated into the red liquid of clarification, and confirms structure by 1H and 13C NMR.
example 5-7, reference examples C1-has the composition of AFM material
Use the acid AFM as shown in example 2-4, by the material mixing shown in table 2 is prepared to composition.Described value be weight %.With MHP, replace AFM material to prepare reference composition C1.
By every kind of resin is coated onto on paper slip, with air cannon, dry up, and then use (the 3M Company of 3M company in Sao Paulo, the 3M cure lamp XL3000(Minnesota State; St.Paul, MN)) solidify and within 80 seconds, carry out solidifying and stress relieving of test composition.
All compositions are solidified into fully curing solid film of indication.It is smooth that example 5-7 keeps after solidifying, and makes contrast curling simultaneously.Smooth is owing to adding acid AFM as stress relieving agent.
table 2
Figure BDA0000466800920000401
the preparation of example 8-AFM-silane
Figure BDA0000466800920000411
By in container by AFM-1(3.00g), 3-isocyanic acid propyl-triethoxysilicane (3.24g) and 1 dibutyl tin laurate mix to prepare AFM-silane.Allow mixture to spend the night in the lower reaction of room temperature (about 23 ℃).By Fourier transform infrared spectroscopy (FTIR) analysis, confirm AFM-silane, thereby isocyanate peak is shown from the loss of silane.
example 9-filler 1
By 50.03g particle B, 4.51g GF-31 silane, 0.77g AFM-silane, 58g ethyl acetate are mixed, and prepare filler by 1.004g30% solution of ammonium hydroxide catalyzed reaction.At room temperature on agitating plate, mixture is stirred and spent the night.In Fume Hoods, flash off solvent the next morning, and at 85 ℃, heat 30 minutes to complete reaction.Described particle comprises 1.5%AFM-silane.
example 10-filler 2
Described in example 9, prepare filler, different is to use 50.00g particle B, 1.27g AFM-silane, 4.01g GF-31 silane, 1.055g30% solution of ammonium hydroxide and 50.7g ethyl acetate.Described particle comprises 2.5%AFM-silane.
example 11-filler 3
As prepared filler in example 9, different is to use 50.07g particle B, 2.51g AFM-silane, 2.753g GF-31,1.041g30% solution of ammonium hydroxide and 50.6g ethyl acetate.Described particle comprises 5%AFM-silane.
example 12-filler 4
As prepared filler in example 9, different is to use 29.98g particle A, 0.965g AFM-silane, 1.61g GF-31 silane, 41.7g ethyl acetate and 0.64g30% solution of ammonium hydroxide.
example 13-14, reference examples C2-paste composition
Dentistry resin combination by stirring the component shown in table 3 until all components dissolves to prepare at about 45 ℃.
table 3
Figure BDA0000466800920000421
Example C2(paste 1) for by 4.40g dentistry resin is mixed to form paste prepared by uniform mixture with 0.82g nanozirconia fillers, 1.5216g nano silicon filler and 13.26g particle B.
Example 13(paste 2) for by by from example 10(filler 2) the paste prepared with formation uniform mixture of 13.26g filler, 0.83g nanozirconia fillers, 1.54g nano silicon filler and 4.4021g dentistry mixed with resin.
Example 14(paste 3) be by the filler of 4.40g dentistry resin, 0.83g nanozirconia fillers, 1.52g nano silicon filler and 13.26g example 11 (filler 3) being mixed to the paste of preparing to form uniform mixture.
According to above-mentioned testing method, to irrigate thatch contraction testing method, the paste of each example is carried out to the test of contraction rate, and with Radial drawing strength testing method, carry out the test of mechanical property.
Contraction rate (ratio by original contraction data falls definite) has been shown in Fig. 1.As from data, along with the content of AFM-silane material increases, contraction rate significantly decline (having found that it meets stress measurement).Paste 1 only comprises GF-31(3-methacryloxypropyl trimethoxy silane), and the amount of paste 2 and 3 AFM-silane on bunch filler increases, described bunch of filler mixes in preparation.
The particle that Radial drawing strength test result in table 4 illustrates through AFM-silane treatment provides the acceptable mechanical property of dental composite.
table 4-Radial drawing strength
Example Radial drawing strength (MPa)
13 80.7
14 76.3
C2 70.9
the preparation of example 15-AFM-caprolactone
Figure BDA0000466800920000441
In being equipped with the 100mL round-bottomed flask of mechanical stirrer, pack AFM-1(32g into, 0.07mol), caprolactone (16g, 0.14mol), stannous octoate (II) (0.05g) and BHT(0.08g), and dry air is flowed through flask to bubbler and condenser.Under continuously stirring, under 130-140C, mixture is stirred to the yellow liquid that spends the night to provide thickness, yield is 95%.NMR confirms structure.
the preparation of oneself interior acyl phosphate of example 16-AFM-
In 500mL3 neck round-bottomed flask, by Vanadium Pentoxide in FLAKES (P 4o 10, 5.10g, 0.0180mol) and be suspended in 10mL CH 2cl 2in.When nitrogen purging, with heat gun, flask is predrying, then under nitrogen, be cooled to room temperature.Flask is also equipped with mechanical stirrer, temperature regulator, and nitrogen gas stream is crossed flask and entered in contiguous bubbler and dropping funnel.In approximately 30 minutes, by the 50mL CH of AFM-caprolactone (24.5g, 0.0358mol) 2cl 2solution slowly adds in suspension.With condenser, replace dropping funnel.Mixture is refluxed 45 minutes.Close heating and be cooled to after room temperature, adding water (0.68g, 0.038mol), recovering subsequently to reflux other 45 minutes.Be cooled to after room temperature, mixture is filtered, be then condensed into yellow oil, wherein yield is 90%. 31p NMR has confirmed the existence of P core.
the preparation of example 17-AFM-trimellitic acid adducts
Under nitrogen, in 3-neck flask, trimellitic acid acid anhydrides chlorine (32.40g, 0.154mol) is dissolved in 100mL acetone.Flask is cooling in ice bath.Solution described in continuously stirring is used dropping funnel by AFM-1(35.25g, 0.0773mol simultaneously) and the 50mL acetone soln of pyridine (12.32g, 0.154mol) slowly add in cooling solution.Complete after interpolation, by flask contents continuously stirring 4 hours at room temperature.Add water (2.77g, 0.154mol) and continue and at room temperature stir and spend the night.Then, by vacuum filtration, remove the solid of formation and use washing with acetone.Filtrate is concentrated and is dried to white solid, wherein yield is 73%.Structure is confirmed by NMR.
the preparation of oneself interior acyl group trimellitic acid of example 18-AFM-
Figure BDA0000466800920000452
Under nitrogen, in 3-neck flask, trimellitic acid acid anhydrides chlorine (50g, 0.240mol) is dissolved in 150mL acetone.Flask is cooling in ice bath.In continuously stirring cooling solution, by drop funnel, slowly add the 80mL acetone soln of AFM-caprolactone intermediate (82.05g, 0.12mol) and pyridine (19.0g, 0.240mol).Complete after interpolation, by flask contents continuously stirring 4 hours at room temperature.Add water (4.32g, 0.240mol) and by solution at room temperature continuously stirring spend the night.By vacuum filtration, remove the solid of formation and use washing with acetone.Filtrate is concentrated and is dried obtain product.
example 19-24, reference examples C3-C4-resin combination
By being mixed to form uniform mixture with the component shown in table 5 and 6, the AFM from example 2,3,4,16 and 17 prepares resin combination.The amount of component be weight %.Prepare example 19-22 and test together with reference examples C3, and prepare example 23-24 and test together with reference examples C4.
According to deflection (stress) amount of above-mentioned test procedure testing tree oil/fat composition, in micron (μ m), and curing depth (DOC), in millimeter (mm).Test result in table 5 and 6 illustrates, and the AFM amount increasing in resin combination has reduced at most advanced and sophisticated deflection in stress test during resin solidification.Curing depth for as for dental composition for acceptable.
table 5
Figure BDA0000466800920000461
table 6
Figure BDA0000466800920000471
example 25-28, reference examples C5-has the nanoparticle fillers of AFM-silane
The composition according to following program preparation with component shown in table 7.Silicon dioxide gel (Nalco2327k) is added in 8 ounces of (235mL) vials with teflon envelope curve, and stir with magnetic stirring bar.Solution is by the AFM-silane mixture of methoxypropanol, Prostab, silane (3-methacryloxypropyl trimethoxy silane) and preparation described in example 8 is prepared in 115mL amber glass bottle, and then adds in silicon dioxide gel and stir through about 5 minutes.
Then with crown cap, teflon band and electrician's band with teflon liner, glass jar is sealed.Under agitation reaction is heated to 90 ℃.After about 18 hours, reaction mixture is transferred in 250mL round-bottomed flask and be concentrated in a vacuum about 45 % by weight solids (being approximately half initial volume).Add about 55 grams of methoxypropanol and get back to about 20 % by weight so that solid reduces.Then solution is concentrated in a vacuum again to about 45 % by weight functionalized nano-particles solids (about 50mL).
According to identical program, prepare reference examples C5, different is by 100 grams of silicon dioxide gel (Nalco2329k colloidal sols; 41.33 % by weight) add 16 ounces (470mL) to have in the glass jar of teflon envelope curve.By the 0.05 % by weight aqueous solution of methoxypropanol (112.5g), Prostab(0.0250g) and the solution of silane (3.182g) add in silicon dioxide gel and stir.Do not add AFM-silane.
The solid weight % of each example is by adding about 0.250g final solution in aluminium dish and dryly in setting the baking oven of 125 ℃ within 45 minutes, determining.Then from baking oven, remove sample, allow it to be cooled to room temperature, and measure the quality of dry sample and for calculating the per-cent of nanoparticles solution solid.Functionalized nano-particles composition is suitable as the filler in resin combination.
table 7
Figure BDA0000466800920000481
example 29-32, reference examples C6-hard coat
Hard coating solution, by 20mL vial, mixes the methoxy propyl alcoholic solution of the functional silicon dioxide nano particle from example 25-28 and C5, pentaerythritol triacrylate, IrgacureTM651 to prepare with the amount shown in table 8.Add methoxypropanol so that the solid weight per-cent of solution reaches 50%.Solution is fully mixed, and supersound process 2-5 minute.
table 8
Figure BDA0000466800920000491
Use #10 kinking rod (to derive from (the RD Specialties of RD Specialties company of New York Robert Webster, Webster, NY)), solution is coated on 6 * 14 inches of thin slices of 5 mil thick PET films (as United States Patent (USP) 6, preparation described in the example 29 of 893,731 (Kausch)).The sample of coating is dried to 30 minutes in the baking oven being set at 75 ℃.Then by using UV treater, (the fusion UV system company of Gaithersburg, the Maryland State (Fusion UV System, Inc., Gaithersburg, MD), with UV lamp (1000mJ/cm 2, UVB) irradiate the film solidify through coating, described UV treater H-lamp is equipped with and under nitrogen environment the linear velocity with 24 feet/min operate (2 times) to provide hard coat on PET film.
After irradiation, measure that film through coat film is curling, hard coat thickness and pencil hardness.The results are shown in table 9.The square sample measurement film of 7.6 * 7.6cm that centre from coat film is cut out is curling.Described sample is placed on flat surfaces, and uses the height at each angle of ruler measurement.Total curling by the height at four angles is sued for peace and determined.
Described film thickness use dial indicator (Mitutoyo Digital Dial Gauge, model is ID-F125E, (the Mitutoyo Corp. of San Feng company of Illinois Ao Luola; Aurora, IL)), at 7.6 * 7.6 each place, angle square and in the middle of each side, measure (altogether measuring for eight times).Use these eight observed values to calculate average film thickness.
According to ASTM D3363, with 7.5N, load, (pencil hardness of each hard coat is measured by the Yi Gao company limited (Elcometer Inc.of Rochester Hills, MI) that derives from Rochester city, the state of Michigan to use Elcometer3086 electric pencil sclerometer.
table 9
Figure BDA0000466800920000501
Figure BDA0000466800920000511
example 33-36, the construction adhesive of reference examples C7-AFM modification
Use AFM-glutarate from example 1 with the amount modification 2-part-structure tackiness agent (DP807) shown in table 9.DP807 tackiness agent provides in duo-pak box.From box, remove each part and for example, mix with the AFM-glutarate of same amount as shown in table 10 (0.38%) respectively.After mixing, each part is reinstalled in its corresponding container in box.Make tackiness agent mix and distribute from box with the ratio of 1:1, make the percent of total of AFM keep identical, for example 0.38%.
According to above-mentioned test procedure, the overlapping shearing resistance of test structure tackiness agent, handling property (degree of wetting and working life) and solidification internal stress.Test structure is illustrated in table 10.The result of overlapping shearing resistance illustrates the acceptable intensity of all tackiness agents, and the degree of wetting of increase for the example that comprises AFM-glutarate and working life.To adding in binder formulation AFM-glutarate to be also illustrated in the remarkable decline of setting up period stress, as by 2.125 " the remarkable decline of the aluminium backing height measured of width place, and curling corresponding of pad reduces indicated.
table 10
Figure BDA0000466800920000512
Figure BDA0000466800920000521
the disclosure provides following illustrative embodiment.
1. addition-clastogen, comprises: 1) unsettled addition-fracture group, 2) group of free redical polymerization, and 3) with the surface modification functional group of the surface association of substrate.
2. according to the addition-clastogen described in embodiment 1, wherein said addition-fracture group 1) be following formula:
Figure BDA0000466800920000522
Wherein
R 2for Z m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl,
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y for its on the functional group that the substrate of described addition-clastogen is associated is set;
M is 1 to 6;
P is 1 or 2;
N is 0 or 1.
3. according to the addition additive of the following formula described in any one in embodiment 1-2:
Figure BDA0000466800920000531
Wherein
R 1, R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group, precondition is R 1, R 2and R 3in at least one be Z m-Q-, and precondition is R 1, R 2and R 3in at least one be Y p-Q '-,
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y for its on the functional group that the substrate of described addition-clastogen is associated is set;
M is 1 to 6;
P is 1 or 2;
Each X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
4. according to the addition-clastogen described in any one in previous embodiment 2 or 3, wherein R 1, R 2and R 3in at least one comprise Z m-Q-and Y p-Q '-both, wherein
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
M is 1 to 6;
P is 1 or 2; And
Y for its on the functional group that the substrate of described addition-clastogen is associated is set.
5. according to the addition-clastogen described in any one in embodiment 2 to 4, wherein Z comprises vinyl, vinyloxy group, (methyl) acryloxy, (methyl) acrylamide, vinylbenzene He Que functional group.
6. according to the linking agent described in any one in embodiment 2 to 5, wherein Z is selected from:
R wherein 4for H or C 1-C 4alkyl.
7. according to the addition-clastogen described in any one in embodiment 2 to 6, be wherein selected from-O-of Q ,-S-,-NR 4-,-SO 2-,-PO 2-,-CO-,-OCO-,-R 6-,-NR 4-CO-NR 4-, NR 4-CO-O-, NR 4-CO-NR 4--CO-O-R 6-,-CO-NR 4-R 6-,-R 6-CO-O-R 6-,-O-R 6-,-S-R 6--,-NR 4-R 6-,-SO 2-R 6-,-PO 2-R 6-,-CO-R 6-,-OCO-R 6-,-NR 4-CO-R 6-, NR 4-R 6-CO-O-and NR 4-CO-NR 4-,
Each R wherein 4for hydrogen, C 1-C 4alkyl group or aromatic yl group, each R 6for having the alkylidene group of 1 to 6 carbon atom, the 5-with 5 to 10 carbon atoms or 6-unit's cycloalkylidene group or having the divalence arylene group of 6 to 16 carbon atoms, precondition is that Q-Z does not comprise peroxide bridge.
8. according to the addition-clastogen described in any one in embodiment 2 to 7, wherein Q is selected from alkylidene group.
9. according to the addition-clastogen described in embodiment 8, wherein Q is formula-C rh 2r-alkylidene group, wherein r is 1 to 10.
10. according to the addition-clastogen described in any one in embodiment 2 to 7, wherein Q is the alkylidene group that hydroxyl replaces.
11. according to the addition-clastogen described in any one in embodiment 2 to 7, and wherein Q is-CH 2-CH (OH)-CH 2-.
12. according to the addition-clastogen described in any one in embodiment 2 to 7, and wherein Q is the alkylidene group that aryloxy replaces.
13. according to the addition-clastogen described in any one in embodiment 2 to 7, and wherein Q is the alkylidene group that alkoxyl group replaces.
14. according to the addition-clastogen described in any one in embodiment 2 to 13, wherein R 1-X 1-group and optionally R 2-X 1-and R 3-X 1-group is selected from H 2c=C (CH 3) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C (CH 3)=CH 2)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH (CH 2oAr)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2cH 2-N (H)-C (O)-O-CH (CH 2oAr)-CH 2-O-., H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and H 2c=C (H) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, wherein Ar is aromatic yl group.
15. according to the addition-clastogen described in any one in embodiment 2 to 14, and wherein Y is phosplate, phosphonic acid ester, phosphonic acids, hydroxamic acid, carboxylic acid and acetylacetic ester, acid anhydrides, isonitrile group, silyl, disulphide, mercaptan, amino,-sulfinic acid, sulfonic acid, phosphine, resol and heterocyclic aromatic group.
16. according to the binder composition described in embodiment 15, the silyl-group that wherein Y is following formula :-SiR 7 3, each R wherein 7group is independently selected from alkoxyl group, acetoxyl group and halogen ion.
17. according to the dental composition described in any one in embodiment 2 to 16, wherein R 1-X 1-group and optionally R 2-X 2-group is selected from H 2c=C (CH 3) C (O)-O-CH 2-CH (O-PO 3h 2)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-C (O)-(CH 2) 3c (O) OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-C (O)-(CH 2) 2c (O) OH)-CH 2-O-and H 2c=C (CH 3) C (O)-O-CH 2-CH (O-C (O)-NH-(CH 2) 3si (OEt) 3)-CH 2-O-.
18. 1 kinds of polymerisable compounds, the monomer that comprises the addition-clastogen described in any one, at least one free redical polymerization in embodiment 1-17 and initiator.
19. according to the polymerisable compound described in embodiment 18, comprises:
A) (methyl) acrylate of 85 to 100 weight parts;
B) sour official's energy ethylenically unsaturated monomers of 0 to 15 weight part;
C) non-sour official's energy ethylenic unsaturated polar monomer of 0 to 10 weight part;
D) 0 to 5 part of vinyl monomer; And
E) in the total monomer of 100 weight parts a) to e), 0 to 5 part of multifunctional (methyl) acrylate; And
F) in 100 weight parts a) to e), the addition-clastogen of 0.1 to 10 weight part.
20. according to the polymerizable compositions described in embodiment 19, also comprises multifunctional (methyl) acrylate of 0.01 to 5 part.
21. according to the polymerisable compound described in any one in embodiment 18 to 20, also comprises light trigger.
22. according to the polymerisable compound described in any one in embodiment 18 to 20, and wherein said initiator is thermal initiator.
23. 1 kinds of methods of preparing addition-clastogen, comprise the compound that makes following formula:
Figure BDA0000466800920000571
X wherein 2comprise electrophilic or nucleophilic functional group,
X 3for X 2, X 1-R 2or X 1-R 3, and
N is 0 or 1;
The step of reacting with the compound of following formula:
Figure BDA0000466800920000572
with
Figure BDA0000466800920000573
Wherein
A 1and A 2respectively do for oneself and the X of functional group 2the functional group of coreaction, R 4for hydrogen, C 1-C 4alkyl group, R 5and R 5* respectively do for oneself ethylenic unsaturated group is engaged to reactive functional groups A 1and A 2singly-bound or divalence or trivalent (mixing) alkyl linking group, and x is 1 or 2.
24. according to the method described in embodiment 23, wherein R 5be selected from the singly-bound or the divalent linker that ethylenic unsaturated group are engaged to co-reactive functional group A.
25. according to the method described in any one in embodiment 23 or 24, wherein R 5be selected from-O-,-S-,-NR 4-,-SO 2-,-PO 2-,-CO-,-OCO-,-NR 4-CO-, NR 4-CO-O-, NR 4-CO-NR 4-,-R 6-and their combination, wherein R 6for thering is the alkylidene group of 1 to 6 carbon atom, the 5-with 5 to 10 carbon atoms or 6-unit's cycloalkylidene group or thering is the divalence arylene group of 6 to 16 carbon atoms.
26. according to the method described in embodiment 18, wherein co-reactive functional group A 1and A 2be selected from separately hydroxyl, amino, azoles quinoline base,
Figure BDA0000466800920000583
oxazolone base, ethanoyl, acetonyl, carboxyl, isocyanato, epoxy group(ing), '-aziridino, acid halide group, vinyloxy group and cyclic anhydride group.
27. according to the method described in any one in embodiment 18 to 26,
As described reactive functional groups X 2during for isocyanato functional group, described co-reactive functional group A 1and A 2each self-contained primary amino or secondary amino group or oh group;
As described reactive functional groups X 2while comprising oh group, described co-reactive functional group A 1and A 2each self-contained carboxyl, ester group, acid halide group, isocyanato, epoxy group(ing), acid anhydrides, azlactone base or
Figure BDA0000466800920000584
azoles quinoline base group;
As described reactive functional groups X 2while comprising carboxylic group, described co-reactive functional group A 1and A 2each self-contained hydroxyl, amino, epoxy group(ing), isocyanato or
Figure BDA0000466800920000585
azoles quinoline base group.
The inorganic oxide of 28. 1 kinds of surface modifications, described inorganic oxide is following formula:
Figure BDA0000466800920000581
Wherein
Filler is inorganic oxide particles,
R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y ' is the residue of described surface modification organo-functional group, described in arranging on itself and its, adds
The substrate of one-tenth-clastogen is associated;
M is 1 to 6;
P is 1 or 2;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
29. 1 kinds of polymerisable compounds, the inorganic oxide of the surface modification of the monomer that comprises at least one free redical polymerization, initiator and embodiment 28.
30. according to the polymerisable compound described in embodiment 18, also comprises the inorganic oxide of the surface modification of following formula:
Figure BDA0000466800920000591
Wherein
Filler is inorganic oxide particles,
R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y ' is the residue of described surface modification organo-functional group, and the substrate that described addition-clastogen is set on itself and its is associated;
M is 1 to 6;
P is 1 or 2;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
31. 1 kinds of hard coating compositions, the addition-clastogen that comprises any one in one or more multifunctional (methyl) acrylate monomers or (methyl) origoester acrylate and embodiment 1 to 17.
32. 1 kinds of hard coating compositions, the addition-clastogen that comprises one or more multifunctional (methyl) acrylate monomers or (methyl) origoester acrylate and embodiment 28 or 29.

Claims (23)

1. addition-clastogen, comprises: 1) unsettled addition-fracture group, 2) group of free redical polymerization, and 3) with the surface modification functional group of the surface association of substrate.
2. addition-clastogen according to claim 1, wherein said addition-fracture group 1) be following formula:
Wherein
R 2for Z m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl,
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y for its on the functional group that the substrate of described addition-clastogen is associated is set;
N is 0 or 1.
3. the addition clastogen of following formula according to claim 1:
Figure FDA0000466800910000012
Wherein
R 1, R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group, precondition is R 1, R 2and R 3in at least one be Z m-Q-, and precondition is R 1, R 2and R 3in at least one be Y p-Q '-,
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y for its on the functional group that the substrate of described addition-clastogen is associated is set;
M is 1 to 6;
P is 1 or 2;
Each X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
4. according to the addition-clastogen described in claim 3 or 4, wherein R 1, R 2and R 3in at least one comprise Z m-Q-and Y p-Q '-both, wherein
Q is covalent linkage or linking group, is preferably (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group, and
Y for its on the functional group that the substrate of described addition-clastogen is associated is set.
5. according to the addition-clastogen described in claim 3 or 4, wherein Z comprises vinyl, vinyloxy group, (methyl) acryloxy, (methyl) acrylamido, vinylbenzene He Que functional group.
6. according to the addition-clastogen described in claim 3 or 4, wherein Q is selected from
-O-,-S-,-NR 4-,-SO 2-,-PO 2-,-CO-,-OCO-,-R 6-,-NR 4-CO-NR 4-, NR 4-CO-O-, NR 4-CO-NR 4--CO-O-R 6-,-CO-NR 4-R 6-,-R 6-CO-O-R 6-,-O-R 6-,-S-R 6--,-NR 4-R 6-,-SO 2-R 6-,-PO 2-R 6-,-CO-R 6-,-OCO-R 6-,-NR 4-CO-R 6-, NR 4-R 6-CO-O-and NR 4-CO-NR 4-,
Each R wherein 4for hydrogen, C 1-C 4alkyl group or aromatic yl group, each R 6for having the alkylidene group of 1 to 6 carbon atom, the 5-with 5 to 10 carbon atoms or 6-unit's cycloalkylidene group or having the divalence arylene group of 6 to 16 carbon atoms, precondition is that Q-Z does not comprise peroxide bridge.
7. according to the addition-clastogen described in claim 3 or 4, wherein Q is alkylidene group.
8. according to the addition-clastogen described in claim 3 or 4, wherein Q is the alkylidene group that hydroxyl replaces.
9. according to the addition-clastogen described in claim 3 or 4, wherein Q is the alkylidene group that aryloxy replaces.
10. according to the addition-clastogen described in claim 3 or 4, wherein Q is the alkylidene group that alkoxyl group replaces.
11. according to addition-clastogen in any one of the preceding claims wherein, wherein R 1-X 1-group and optionally R 2-X 1-and R 3-X 1-group is selected from H 2c=C (CH 3) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C (CH 3)=CH 2)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH (CH 2oAr)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2cH 2-N (H)-C (O)-O-CH (CH 2oAr)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (CH 3) C (O)-O-CH 2-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and H 2c=C (H) C (O)-O-CH 2-CH (OH)-CH 2-O-, H 2c=C (H) C (O)-O-(CH 2) 4-O-CH 2-CH (O-(O) C (H)=CH 2)-CH 2-O-and CH 3-(CH 2) 7-CH (O-(O) C-N (H)-CH 2cH 2-O-(O) C (CH 3) C=CH 2)-CH 2-O-, wherein Ar is aromatic yl group.
12. according to addition-clastogen in any one of the preceding claims wherein, and wherein Y is phosplate, phosphonic acid ester, phosphonic acids, hydroxamic acid, carboxylic acid and acetylacetic ester, acid anhydrides, isonitrile group, silyl, disulphide, mercaptan, amino,-sulfinic acid, sulfonic acid, phosphine, resol or heterocyclic aromatic group.
13. binder compositions according to claim 15, the silyl-group that wherein Y is following formula :-SiR 7 3, each R wherein 7group is independently selected from alkoxyl group, acetoxyl group and halogen ion.
14. 1 kinds of polymerisable compounds, the monomer that comprises the addition-clastogen described in any one, at least one free redical polymerization in claim 1-13 and initiator.
15. polymerisable compounds according to claim 14, comprise:
A) (methyl) acrylate of 85 to 100 weight parts;
B) sour official's energy ethylenically unsaturated monomers of 0 to 15 weight part;
C) non-sour official's energy ethylenic unsaturated polar monomer of 0 to 10 weight part;
D) 0 to 5 part of vinyl monomer; And
E) in 100 weight part total monomers a) to e), 0 to 5 part of multifunctional (methyl) acrylate; And
F) in 100 weight parts a) to e), the addition-clastogen of 0.1 to 10 weight part.
16. polymerizable compositions according to claim 15, also comprise multifunctional (methyl) acrylate of 0.01 to 5 part.
17. according to claim 14 to the polymerisable compound described in any one in 16, also comprises the inorganic oxide of the surface modification of following formula:
Figure FDA0000466800910000041
Wherein
Filler is inorganic oxide particles,
R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y ' is the residue of described surface modification organo-functional group, and the substrate that described addition-clastogen is set on itself and its is associated;
M is 1 to 6;
P is 1 or 2;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
18. 1 kinds of methods of preparing the addition-clastogen described in any one in claim 3 to 13, comprise the compound that makes following formula:
Figure FDA0000466800910000051
X wherein 2comprise electrophilic or nucleophilic functional group,
X 3for X 2, X 1-R 2or X 1-R 3, and
N is 0 or 1;
The step of reacting with the compound of following formula:
Figure FDA0000466800910000061
with
Figure FDA0000466800910000062
Wherein
A 1and A 2respectively do for oneself and the X of functional group 2the functional group of coreaction, R 4for hydrogen, C 1-C 4alkyl group, R 5and R 5* respectively do for oneself ethylenic unsaturated group is engaged to reactive functional groups A 1and A 2singly-bound or divalence or trivalent (mixing) alkyl linking group, and x is 1 or 2.
19. method according to claim 17, wherein R 5be selected from the singly-bound or the divalent linker that ethylenic unsaturated group are engaged to co-reactive functional group A.
20. methods according to claim 18,
As described reactive functional groups X 2during for isocyanato functional group, described co-reactive functional group A 1and A 2each self-contained primary amino or secondary amino group or oh group;
As described reactive functional groups X 2while comprising oh group, described co-reactive functional group A 1and A 2each self-contained carboxyl, ester group, acid halide group, isocyanato, epoxy group(ing), acid anhydrides, azlactone base or
Figure FDA0000466800910000063
azoles quinoline base group;
As described reactive functional groups X 2while comprising carboxylic group, described co-reactive functional group A 1and A 2each self-contained hydroxyl, amino, epoxy group(ing), isocyanato or
Figure FDA0000466800910000064
azoles quinoline base group.
The inorganic oxide of 21. 1 kinds of surface modifications, described inorganic oxide is following formula:
Figure FDA0000466800910000065
Wherein
Filler is inorganic oxide particles,
R 2and R 3be Z independently of one another m-Q-, Y p-Q '-, (mixing) alkyl group or (mixing) aromatic yl group;
Q is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with m+1 valency;
Q ' is covalent linkage or linking group, is preferably organic (mixing) alkyl linking group with p+1 valency;
Z is ethylenic unsaturated polymerizable group,
Y ' is the residue of described surface modification organo-functional group, and the substrate that described addition-clastogen is set on itself and its is associated;
M is 1 to 6;
P is 1 or 2;
X 1be independently-O-or-NR 4-, R wherein 4for H or C 1-C 4alkyl, and
N is 0 or 1.
22. 1 kinds of hard coating compositions, the addition-clastogen that comprises any one in one or more multifunctional (methyl) acrylate monomers or (methyl) origoester acrylate and claim 1 to 13 or 20.
23. 1 kinds of hard coating compositions, the addition-clastogen that comprises one or more multifunctional (methyl) acrylate monomers or (methyl) origoester acrylate and claim 20.
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